A scattering-foil free electron beam to increase dose rate for total skin electron therapy (TSET).

BACKGROUND: Electron beams are used at extended distances ranging between 300 to 700 cm to uniformly cover the entirety of the patient's skin for total skin electron therapy (TSET). Even with electron beams utilizing the high dose rate total skin electron (HDTSe) mode from the Varian 23iX or TrueBeam accelerators, the dose rate is only 2500 cGy/min at source-to-surface distance (SSD) = 100 cm. At extended distances, the decrease in dose rate leads to long beam delivery times that can limit or even prevent the use of the treatment for patients who, in their weakened condition, may be unable to stand on their own for extended periods of time. Previously, to increase dose rate, a customized 6 MeV electron beam was created by removing the x-ray target, flattening filter, beam monitor chamber, and so forth. from the beam path (Chen, et at IJROBP 59, 2004) for TSET. Using this scattering-foil free (SFF) electron beam requires the treatment distance be extended to 700 cm to achieve dose uniformity from the single beam. This room size requirement has limited the widespread use of the 6 MeV-SFF beam. PURPOSE: This study explores an application of a dual-field technique with a 6 MeV-SFF beam to provide broad and uniform electron fields to reduce the treatment distances in order to overcome treatment room size limitations. METHODS: The EGSnrc system was used to generate incident beams. Gantry angles between 6 MeV-SFF dual-fields were optimized to achieve the similar patient skin dose distribution resulting from a standard 6 MeV-HDTSe dual-field configuration. The patient skin dose comparisons were performed based on the patient treatment setup geometries using dose-volume-histograms. RESULTS: Similar dose coverage can be achieved between 6 MeV-SFF and 6 MeV-HDTSe beams by reducing gantry angles between dual-field geometries by 8° and 7° at treatment distances of 400 and 500 cm, respectively. To achieve 95% mean dose to the first 5 mm of skin depth in the torso area, the mean dose to depths of 5-10 mm and 10-15 mm below the skin surface was 74% (74%) and 49% (50%) of the prescribed dose when using 6 MeV-SFF (6 MeV-HDTSe) beam, respectively. CONCLUSIONS: The 6 MeV-SFF electron beam is feasible to provide similar TSET skin dose coverage at SSD ≥ 400 cm using a dual-field technique. The dose rate of the 6 MeV-SFF beam is about 4 times that of current available 6 MeV-HDTSe beams at treatment distances of 400-500 cm, which significantly shortens the treatment beam-on time and makes TSET available to patients in weakened conditions.

Shared genetic aetiology of respiratory diseases: a genome-wide multitraits association analysis.

OBJECTIVE: This study aims to explore the common genetic basis between respiratory diseases and to identify shared molecular and biological mechanisms. METHODS: This genome-wide pleiotropic association study uses multiple statistical methods to systematically analyse the shared genetic basis between five respiratory diseases (asthma, chronic obstructive pulmonary disease, idiopathic pulmonary fibrosis, lung cancer and snoring) using the largest publicly available genome wide association studies summary statistics. The missions of this study are to evaluate global and local genetic correlations, to identify pleiotropic loci, to elucidate biological pathways at the multiomics level and to explore causal relationships between respiratory diseases. Data were collected from 27 November 2022 to 30 March 2023 and analysed from 14 April 2023 to 13 July 2023. MAIN OUTCOMES AND MEASURES: The primary outcomes are shared genetic loci, pleiotropic genes, biological pathways and estimates of genetic correlations and causal effects. RESULTS: Significant genetic correlations were found for 10 paired traits in 5 respiratory diseases. Cross-Phenotype Association identified 12 400 significant potential pleiotropic single-nucleotide polymorphism at 156 independent pleiotropic loci. In addition, multitrait colocalisation analysis identified 15 colocalised loci and a subset of colocalised traits. Gene-based analyses identified 432 potential pleiotropic genes and were further validated at the transcriptome and protein levels. Both pathway enrichment and single-cell enrichment analyses supported the role of the immune system in respiratory diseases. Additionally, five pairs of respiratory diseases have a causal relationship. CONCLUSIONS AND RELEVANCE: This study reveals the common genetic basis and pleiotropic genes among respiratory diseases. It provides strong evidence for further therapeutic strategies and risk prediction for the phenomenon of respiratory disease comorbidity.

A late-Ediacaran crown-group sponge animal.

Sponges are the most basal metazoan phylum1 and may have played important roles in modulating the redox architecture of Neoproterozoic oceans2. Although molecular clocks predict that sponges diverged in the Neoproterozoic era3,4, their fossils have not been unequivocally demonstrated before the Cambrian period5-8, possibly because Precambrian sponges were aspiculate and non-biomineralized9. Here we describe a late-Ediacaran fossil, Helicolocellus cantori gen. et sp. nov., from the Dengying Formation (around 551-539 million years ago) of South China. This fossil is reconstructed as a large, stemmed benthic organism with a goblet-shaped body more than 0.4 m in height, with a body wall consisting of at least three orders of nested grids defined by quadrate fields, resembling a Cantor dust fractal pattern. The resulting lattice is interpreted as an organic skeleton comprising orthogonally arranged cruciform elements, architecturally similar to some hexactinellid sponges, although the latter are built with biomineralized spicules. A Bayesian phylogenetic analysis resolves H. cantori as a crown-group sponge related to the Hexactinellida. H. cantori confirms that sponges diverged and existed in the Precambrian as non-biomineralizing animals with an organic skeleton. Considering that siliceous biomineralization may have evolved independently among sponge classes10-13, we question the validity of biomineralized spicules as a necessary criterion for the identification of Precambrian sponge fossils.

ZnSeTe quantum dots modified with zinc chloride toward bright trap-state emission.

ZnSeTe quantum dots (QDs) attract growing interest owing to their low threats to health and the environment. They are widely applied as emitters in displays and lighting devices. Previous findings have indicated that inorganic halides are excellent candidates for surface ligands on QDs. By incorporating inorganic halides during the synthesis process, the photoluminescence (PL) intensity and quantum yield (QY) of QDs can be significantly enhanced. However, the alteration of surface states in QDs induced by zinc halide modification and the mechanism of formation of trap-state radiative recombination processes have been less discussed. Herein, we proposed a synthesis strategy for ZnSeTe/ZnSe/ZnSeS/ZnS core/shell/shell/shell QDs modified with ZnCl2, and by comparing the morphology and elemental composition of QDs with different amounts of ZnCl2 added, we revealed the regulatory mechanism of nanocrystal growth in the presence of ZnCl2. QDs with modification of ZnCl2 exhibited broad yellow fluorescence, distinct from the intrinsic blue emission. Through spectroscopic and surface ligand analyses, we attributed this yellow emission to the intermediate state energy levels caused by the defects on the surface. Finally, we used the QDs with broad linewidth emission to fabricate a simple white-light-emitting diode (WLED). This work provided new insights into the role of inorganic ligands and the use of a single emitting material in solid-state lighting devices.

Serum iron level is independently associated with sarcopenia: a retrospective study.

Sarcopenia greatly reduces the quality of life of the elderly, and iron metabolism plays an important role in muscle loss. This study aimed to investigate the association between iron status and sarcopenia. A total of 286 adult patients hospitalized between 2019 and 2021 were included in this study, of which 117 were diagnosed with sarcopenia. Serum iron, total iron binding capacity (TIBC), transferrin, and transferrin saturation levels were compared between groups with and without sarcopenia and were included in the logistic analyses, with significant variables further included in the logistic regression model for the prediction of sarcopenia. Serum iron, TIBC, and transferrin levels decreased significantly in the sarcopenia group (p < 0.05), and were negatively associated with handgrip strength, relative skeletal muscle index, and multiple test performances (p < 0.05). Multivariate logistic analysis showed that sex, age, body mass index (BMI), and serum iron level were independent risk factors for sarcopenia. In the final logistic regression model, male sex (odds ratio [OR] 3.65, 95% confidence interval [CI] 1.67-7.98), age > 65 years (OR 5.40, 95% CI 2.25-12.95), BMI < 24 kg/m2 (OR 0.17, 95% CI 0.08-0.36), and serum iron < 10.95 µmol/L (OR 0.39, 95% CI 0.16-0.93) were included. Our study supported the impact of iron metabolism on muscle strength and performance.

How do e-commerce platforms and retailers implement discount pricing policies under consumers are strategic?

In the era of the rapid development of e-commerce, many retailers choose to launch promotional activities to become consumers' first choice for shopping. Since price discounts can greatly attract consumers, the e-commerce platforms have also begun to implement discount pricing. It is urgent for e-commerce platforms and retailers to formulate reasonable discount strategies to achieve sustainable business. In this paper, we construct a dynamic game model for implementing discount pricing on an e-commerce platform and two retailers, we study the market equilibrium between the two retailers and the e-commerce platform under various scenarios that considering consumers' strategic waiting behavior and competition between the two retailers, we further discuss the effectiveness of retailer discount pricing and the double discount pricing of the platform and retailers. We show that the optimal pricing decreases as the difference in product quality narrows under both pricing strategies. Low-quality retailers implementing a double discount pricing strategy are in relatively higher demand only when the difference in product quality is small. High-quality retailers implementing the retailer discount pricing strategy are in relatively higher demand only when the product quality difference is large. Double discount pricing is desirable for both e-commerce platforms and retailers and can be used to effectively achieve Pareto improvement in the market by increasing their expected profit. Our results emphasize the role of product quality and the value of the double discount pricing strategy. The double discount pricing strategy weakens the profit advantage that retailers and platforms gain from it as the rebate intensity and rebate redemption rates increase.

Understanding the Novel Approach of Nanoferroptosis for Cancer Therapy.

As a new form of regulated cell death, ferroptosis has unraveled the unsolicited theory of intrinsic apoptosis resistance by cancer cells. The molecular mechanism of ferroptosis depends on the induction of oxidative stress through excessive reactive oxygen species accumulation and glutathione depletion to damage the structural integrity of cells. Due to their high loading and structural tunability, nanocarriers can escort the delivery of ferro-therapeutics to the desired site through enhanced permeation or retention effect or by active targeting. This review shed light on the necessity of iron in cancer cell growth and the fascinating features of ferroptosis in regulating the cell cycle and metastasis. Additionally, we discussed the effect of ferroptosis-mediated therapy using nanoplatforms and their chemical basis in overcoming the barriers to cancer therapy.

Pollinator shift ensures reproductive success in a camouflaged alpine plant.

BACKGROUND AND AIMS: There are intrinsic conflicts between signalling to mutualists and concealing (camouflaging) from antagonists. Like animals, plants also use camouflage as a defence against herbivores. However, this can potentially reduce their attractiveness to pollinators. METHODS: Using Fritillaria delavayi, an alpine camouflaged plant with inter-population floral colour divergence, we tested the influence of floral trait differences on reproduction. We conducted pollination experiments, measured floral morphological characteristics, estimated floral colours perceived by pollinators, analysed floral scent, and investigated the reproductive successes in five populations. KEY RESULTS: We found that the reproduction of F. delavayi depends on pollinators. Under natural conditions, a flower-camouflaged population had a 100% fruit set and similar seed set to three out of four yellow-flowered populations. Bumblebees are important pollinators in the visually conspicuous yellow-flowered populations, whereas flies are the only pollinator in the flower-camouflaged population, visiting flowers more frequently than bumblebees. The camouflaged flowers cannot be discriminated from the rock background as perceived by pollinators, but may be located by flies through olfactory cues. CONCLUSIONS: Collectively, our results demonstrate that the flower-camouflaged population has different reproductive traits from the visually conspicuous yellow-flowered ones. A pollinator shift from bumblebees to flies, combined with high visitation frequency, compensates the attractiveness disadvantage in camouflaged plants.

Multidrug resistance transporters P-gp and BCRP limit the efficacy of ATR inhibitor ceralasertib in cancer cells.

The therapeutic effect of chemotherapy and targeted therapy are known to be limited by drug resistance. Substantial evidence has shown that ATP-binding cassette (ABC) transporters P-gp and BCRP are significant contributors to multidrug resistance (MDR) in cancer cells. In this study, we demonstrated that a clinical-staged ATR inhibitor ceralasertib is susceptible to P-gp and BCRP-mediated MDR. The drug resistant cancer cells were less sensitive to ceralasertib compared to the parental cells. Moreover, ceralasertib resistance can be reversed by inhibiting the drug efflux activity of P-gp and BCRP. Interestingly, ceralasertib was able to downregulate the level of P-gp but not BCRP, suggesting a potential regulation between ATR signaling and P-gp expression. Furthermore, computational docking analysis predicted high affinities between ceralasertib and the drug-binding sites of P-gp and BCRP. In summary, overexpression of P-gp and BCRP are sufficient to confer cancer cells resistance to ceralasertib, underscoring their role as biomarkers for therapeutic efficacy.

Reconfigurable 4D printing via mechanically robust covalent adaptable network shape memory polymer.

4D printing enables 3D printed structures to change shape over "time" in response to environmental stimulus. Because of relatively high modulus, shape memory polymers (SMPs) have been widely used for 4D printing. However, most SMPs for 4D printing are thermosets, which only have one permanent shape. Despite the efforts that implement covalent adaptable networks (CANs) into SMPs to achieve shape reconfigurability, weak thermomechanical properties of the current CAN-SMPs exclude them from practical applications. Here, we report reconfigurable 4D printing via mechanically robust CAN-SMPs (MRC-SMPs), which have high deformability at both programming and reconfiguration temperatures (>1400%), high Tg (75°C), and high room temperature modulus (1.06 GPa). The high printability for DLP high-resolution 3D printing allows MRC-SMPs to create highly complex SMP 3D structures that can be reconfigured multiple times under large deformation. The demonstrations show that the reconfigurable 4D printing allows one printed SMP structure to fulfill multiple tasks.

KLF4 Inhibits the Activation of Human Hepatic Stellate Cell In Vitro.

OBJECTIVE: Hepatic stellate cells (HSCs) play a crucial role in liver fibrosis. Early-stage liver fibrosis is reversible and intimately associated with the state of HSCs. Kruppel-like factor 4 (KLF4) plays a pivotal role in a wide array of physiological and pathological processes. This study aimed to investigate the effect of KLF4 on the proliferation, apoptosis and phenotype of quiescent HSCs METHODS: We designed a KLF4 lentiviral vector and a KLF4 siRNA lentiviral vector, to upregulate and silence KLF4 expression in human HSC LX-2 cells via transfection. Cell proliferation was assessed using the CCK-8 assay. Flow cytometry was used to detect the cell cycle distribution and apoptosis rate. Western blotting was used to determine the levels of some quiescence and activation markers of HSCs RESULTS: Overexpression of KLF4 significantly increased the levels of E-cadherin and ZO-1, which are quiescent HSC markers, while significantly decreased the levels of N-cadherin and a-SMA, known activated HSC markers. In contrast, cell proliferation and apoptosis rates were elevated in LX-2 cells in which KLF4 expression was silenced CONCLUSION: KLF4 inhibits the proliferation and activation of human LX-2 HSCs. It might be a key regulatory protein in the maintenance of HSC quiescence and may serve as a target for the inhibition of hepatic fibrosis.

Bioinformatics investigation of adaptive immune-related genes in peri-implantitis and periodontitis: Characteristics and diagnostic values.

BACKGROUND: Peri-implantitis and periodontitis have similar immunological bioprocesses and inflammatory phenotypes. In the inflammatory process, the adaptive immune cells can drive the development of disease. This research investigated the differences and diagnostic significance of peri-implantitis and periodontitis in adaptive immune responses. METHODS: We acquired four GEO datasets of gene expressions in surrounding tissues in healthy person, healthy implant, periodontitis, and peri-implantitis patients. The structural characteristics and enrichment analyses of differential expression genes were examined. The adaptive immune landscapes in peri-implantitis and periodontitis were then evaluated using single sample gene set enrichment analysis. The STRING database and Cytoscape were used to identify adaptive hub genes, and the ROC curve was used to verify them. Finally, qRT-PCR method was used to verify the expression level of Hub gene in activated T cells on the titanium-containing or titanium-free culture plates. RESULTS: At the transcriptome level, the data of healthy implant, peri-implantitis and periodontitis were highly dissimilar. The peri-implantitis and periodontitis both exhibited adaptive immune response. Except for the activated CD4+T cells, there was no significant difference in other adaptive immune cells between peri-implantitis and periodontitis. In addition, correlation analysis showed that CD53, CYBB, and PLEK were significantly positively linked with activated CD4+T cells in the immune microenvironment of peri-implantitis, making them effective biomarkers to differentiate it from periodontitis. CONCLUSIONS: Peri-implantitis has a uniquely immunogenomic landscape that differs from periodontitis. This study provides new insights and ideas into the activated CD4+T cells and hub genes that underpin the immunological bioprocess of peri-implantitis.

Neurons dispose of hyperactive kinesin into glial cells for clearance.

Microtubule-based kinesin motor proteins are crucial for intracellular transport, but their hyperactivation can be detrimental for cellular functions. This study investigated the impact of a constitutively active ciliary kinesin mutant, OSM-3CA, on sensory cilia in C. elegans. Surprisingly, we found that OSM-3CA was absent from cilia but underwent disposal through membrane abscission at the tips of aberrant neurites. Neighboring glial cells engulf and eliminate the released OSM-3CA, a process that depends on the engulfment receptor CED-1. Through genetic suppressor screens, we identified intragenic mutations in the OSM-3CA motor domain and mutations inhibiting the ciliary kinase DYF-5, both of which restored normal cilia in OSM-3CA-expressing animals. We showed that conformational changes in OSM-3CA prevent its entry into cilia, and OSM-3CA disposal requires its hyperactivity. Finally, we provide evidence that neurons also dispose of hyperactive kinesin-1 resulting from a clinic variant associated with amyotrophic lateral sclerosis, suggesting a widespread mechanism for regulating hyperactive kinesins.

Intraspecific floral colour variation in three Pedicularis species.

Flower constancy describes the phenomenon that pollinators tend to successively visit flowers of a single species during foraging, reducing reproductive interference in natural communities. The extent of flower constancy is largely determined by the floral traits of co-flowering species. Both higher inter-specific and lower intraspecific differences of floral traits should contribute to a higher level of flower constancy. However, previous studies mainly focused on interspecific difference, and the intraspecific variation (consistency) of floral traits received much less attention. We hypothesise that selection may favour lower intraspecific floral trait variation in communities composed of multiple co-flowering congeners. We investigated the floral colour variation of three focal Pedicularis species that share pollinators in 19 communities composed of either single or multiple Pedicularis species. Colour was quantified using image-based colour analysis as perceived by pollinators. We found that most of the intrapopulation floral colour variation was below the colour discrimination threshold of bumblebees, implying strongly constrained by the visual selection by pollinators. Contrary to the hypothesis, there is no significant difference in intraspecific floral colour variation between different community contexts. It may be due to the relatively large interspecific floral colour differences of most co-flowering species. The influence of community context on intraspecific variation may be reflected in floral traits other than colours.

Small extracellular vesicles (sEVs)-based gene delivery platform for cell-specific CRISPR/Cas9 genome editing.

Small extracellular vesicles (sEVs) are naturally occurring vesicles that have the potential to be manipulated to become promising drug delivery vehicles for on-demand in vitro and in vivo gene editing. Here, we developed the modular safeEXO platform, a prototype sEV delivery vehicle that is mostly devoid of endogenous RNA and can efficaciously deliver RNA and ribonucleoprotein (RNP) complexes to their intended intracellular targets manifested by downstream biologic activity. We also successfully engineered producer cells to produce safeEXO vehicles that contain endogenous Cas9 (safeEXO-CAS) to effectively deliver efficient ribonucleoprotein (RNP)-mediated CRISPR genome editing machinery to organs or diseased cells in vitro and in vivo. We confirmed that safeEXO-CAS sEVs could co-deliver ssDNA, sgRNA and siRNA, and efficaciously mediate gene insertion in a dose-dependent manner. We demonstrated the potential to target safeEXO-CAS sEVs by engineering sEVs to express a tissue-specific moiety, integrin alpha-6 (safeEXO-CAS-ITGA6), which increased their uptake to lung epithelial cells in vitro and in vivo. We tested the ability of safeEXO-CAS-ITGA6 loaded with EMX1 sgRNAs to induce lung-targeted editing in mice, which demonstrated significant gene editing in the lungs with no signs of morbidity or detectable changes in immune cell populations. Our results demonstrate that our modular safeEXO platform represents a targetable, safe, and efficacious vehicle to deliver nucleic acid-based therapeutics that successfully reach their intracellular targets. Furthermore, safeEXO producer cells can be genetically manipulated to produce safeEXO vehicles containing CRISPR machinery for more efficient RNP-mediated genome editing. This platform has the potential to improve current therapies and increase the landscape of treatment for various human diseases using RNAi and CRISPR approaches.

Non-allergic eosinophilic inflammation and airway hyperresponsiveness induced by diesel engine exhaust through activating ILCs.

RATIONALE: Diesel engine exhaust (DEE) is associated with the development and exacerbation of asthma. Studies have shown that DEE can aggravate allergen-induced eosinophilic inflammation in lung. However, it remains not clear that whether DEE alone could initiate non-allergic eosinophilic inflammation and airway hyperresponsiveness (AHR) through innate lymphoid cells (ILCs) pathway. OBJECTIVE: This study aims to investigate the airway inflammation and hyperresponsiveness and its relationship with ILC after DEE exposure. METHOD: Non-sensitized BALB/c mice were exposed in the chamber of diesel exhaust or filtered air for 2, 4, and 6 weeks (4 h/day, 6 days/week). Anti-CD4 mAb or anti-Thy1.2 mAb was administered by intraperitoneal injection to inhibit CD4+T or ILCs respectively. AHR、airway inflammation and ILCs were assessed. RESULT: DEE exposure induced significantly elevated level of neutrophils, eosinophils, collagen content at 4, 6 weeks. Importantly, the airway AHR was only significant in the 4weeks-DEE exposure group. No difference of the functional proportions of Th2 cells was found between exposure group and control group. The proportions of IL-5+ILC2, IL-17+ILC significantly increased in 2, 4weeks-DEE exposure group. After depletion of CD4+T cells, both the proportion of IL-5+ILC2 and IL-17A ILCs was higher in the 4weeks-DEE exposure group which induced AHR, neutrophilic and eosinophilic inflammation accompanied by the IL-5, IL-17A levels. CONCLUSION: Diesel engine exhaust alone can imitate asthmatic characteristics in mice model. Lung-resident ILCs are one of the major effectors cells responsible for a mixed Th2/Th17 response and AHR.

Pixel-wise programmability enables dynamic high-SNR cameras for high-speed microscopy.

High-speed wide-field fluorescence microscopy has the potential to capture biological processes with exceptional spatiotemporal resolution. However, conventional cameras suffer from low signal-to-noise ratio at high frame rates, limiting their ability to detect faint fluorescent events. Here, we introduce an image sensor where each pixel has individually programmable sampling speed and phase, so that pixels can be arranged to simultaneously sample at high speed with a high signal-to-noise ratio. In high-speed voltage imaging experiments, our image sensor significantly increases the output signal-to-noise ratio compared to a low-noise scientific CMOS camera (~2-3 folds). This signal-to-noise ratio gain enables the detection of weak neuronal action potentials and subthreshold activities missed by the standard scientific CMOS cameras. Our camera with flexible pixel exposure configurations offers versatile sampling strategies to improve signal quality in various experimental conditions.

VISTA: A Novel Checkpoint for Cancer Immunotherapy.

V-domain Ig suppressor of T cell activation (VISTA) is a recently identified member of the B7 family of immunoregulatory proteins. It is pivotal for maintaining T cell quiescence and exerts a significant regulatory influence on the immune response to tumors. Accumulating clinical evidence suggests that the influence of VISTA on tumor immunity is more nuanced than initially postulated. Although these revelations add layers of complexity to our understanding of the function of VISTA, they also offer novel avenues for scientific inquiry and potential therapeutic targets. In this review, we scrutinize the current literature pertaining to the expression of VISTA in various of malignancies, aiming to elucidate its intricate roles within the tumor microenvironment and in cancer immunotherapy.

Characterization of mechanical stress in the occurrence of cortical opacification in age-related cataracts using three-dimensional finite element model of the human lens and RNA-seq.

Cataract is the leading cause of blindness across the world. Age-related cataract (ARC) is the most common type of cataract, but its pathogenesis is not fully understood. Using three-dimensional finite element modeling combining experimental biotechnology, our study demonstrates that external forces during accommodation cause mechanical stress predominantly in lens cortex, basically matching the localization of opacities in cortical ARCs. We identified the cellular senescence and upregulation of PIEZO1 mRNA in HLECs under mechanical stretch. This mechano-induced senescence in HLECs might be mediated by PIEZO1-related pathways, portraying a potential biomechanical cause of cortical ARCs. Our study updates the fundamental insight towards cataractogenesis, paving the way for further exploration of ARCs pathogenesis and nonsurgical treatment.

Theoretical simulation of TADF character of 3,9'-bicarbazole-modified 2,4,6-triphenyl-1,3,5-triazine.

CONTEXT: Three donor (D)-acceptor (A)-type temperature-activated delayed fluorescent (TADF) molecules of 9-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (o-TrzDCz), 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (m-TrzDCz), and 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9'-bicarbazole (p-TrzDCz) were designed in this paper, and the photophysical properties, including the intersystem crossing rate, the reorganization energies (λ), and the intersystem crossing/reverse intersystem crossing (ISC/RISC) rate, were simulated to explore the effect of substitution sites on their TADF character. The values of the twist angle between the D and A moieties in ground state and the molecular root-mean-square deviation (RMSD) of the S1 and T1 states referenced to the S0 state indicate that o-TrzDCz possess bigger steric hindrance and stabler molecular configuration. The λ values of the ISC/RISC process should be 0.06/0.04 eV for o-TrzDCz, which are much smaller than those of m-TrzDCz (0.51/0.41 eV) and p-TrzDCz (1.93/1.06 eV). At the same time, o-TrzDCz possess the biggest kRISC (7.28 × 106 s-1) and kr (3.12 × 106 s-1) values and the smallest kp (0.10 s-1) value among the three titled molecules. These data indicate that o-TrzDCz should have more excellent TADF character than m-TrzDCz and p-TrzDCz. In a word, this research presents that adjusting the molecular linking manner should be a charming way to explore novel high-efficient TADF molecules. METHODS: Quantum chemical calculations were performed at PBE0/6-31G* level by Gaussian 09 and ORCA 4.1.0 software packages, and reorganization energies and Huang-Rhys were performed by the DUSHIN program and MOMAP 2019B software package based on the Gaussian 09 output files, while the phosphorescence rates were performed at B3LYP/6-31G* level by Dalton 2021.