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Three novel asymmetric Ir(III) complexes have been rationally designed to optimize their emitting dipole orientations (EDO) and enhance light outcoupling in blue phosphorescent organic light-emitting diodes (OLEDs), thereby boosting their external quantum efficiency (EQE). Bulky electron-donating groups (EDGs), namely: carbazole (Cz), di-tert-butyl carbazole (tBuCz), and phenoxazine (Pxz) are incorporated into the tridentate dicarbene pincer chelate to induce high degree of packing anisotropy, simultaneously enhancing their photophysical properties. Angle-dependent photoluminescence (ADPL) measurements indicate increased horizontal transition dipole ratios of 0.89 and 0.90 for the Ir(III) complexes Cz-dfppy-CN and tBuCz-dfppy-CN, respectively. Analysis of the single crystal structure and density functional theory (DFT) calculation results revealed an inherent correlation between molecular aspect ratio and EDO. Utilizing the newly obtained emitters, the blue OLED devices demonstrated exceptional performance, achieving a maximum EQE of 30.7% at a Commission International de l'Eclairage (CIE) coordinate of (0.140, 0.148). Optical transfer matrix-based simulations confirmed a maximum outcoupling efficiency of 35% due to improved EDO. Finally, the tandem OLED and hyper-OLED devices exhibited a maximum EQE of 44.2% and 31.6%, respectively, together with good device stability. This rational molecular design provides straightforward guidelines to reach highly efficient and stable saturated blue emission.
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A promising kind of ternary chiral co-assemblies with high PLQY, large dissymmetry factor (glum), and narrowband multi-resonance characteristics are achieved by codoped-thermal annealing treatments of achiral luminescent polymer F8BT, chiral inducers R/S-5011, and achiral FRET acceptor DBN-ICZ. The optimized co-assemblies (F8BT)0.9-(R/S-5011)0.1-(DBN-ICZ)0.005 display narrowband yellow emission with full-width half maximum (FWHM) of 37 nm, PLQY of 79%, and intense CPL signals with |glum| of up to 0.26. Meaningfully, solution-processed CP-OLEDs by using those ternary chiral co-assemblies as emitting layer are successfully fabricated, which display yellow circularly polarized electroluminescence (CPEL) with EQEmax of 4.6% and gEL of up to 0.16. The corresponding Q-factor could reach up to 7.36 × 10-3, which is the highest of all the reported CP-OLEDs. Moreover, the devices also exhibit excellent comprehensive device performance with low Von of 7.0 V, high Lmax of about 25 000 cd m-2, extremely low efficiency roll-off with EQE of 4.3% at 10 000 cd m-2, as well as narrowband EL with FWHM of only 39 nm. The proposed ternary co-assembly strategy in fabricating CP-OLED provides the possibility to achieve high comprehensive device performance such as balancing high EQE and large gEL value, as well as narrowband emission, high brightness and low efficiency roll-off simultaneously.
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Thermally activated delayed fluorescence (TADF) emitters with a high horizontal orientation are highly essential for improving the external quantum efficiency (EQE) of organic light-emitting diodes; however, pivotal molecular design strategies to improve the horizontal orientation of solution processable TADF emitters are still scarce and challenging. Herein, a phenyl bridge is adopted to connect the double TADF units, and a dimerized TADF dendrimer, D4CzBNPh-SF, is successfully constructed. Compared to counterpart with single TADF unit, the proof-of-the-concept molecule not only exhibits an improved horizontal dipole ratio (78%) due to the π-delocalization-induced extended molecular conjugation, but also displays a faster reversed intersystem crossing rate constant (6.08×106 s-1) and a high photoluminescence quantum yield of 95% in neat film. Consequently, the non-doped solution-processed device with D4CzBNPh-SF as the emitter, achieves an ultra-high maximum EQE of 32.6%, which remains at 26.6% under a luminance of 1000 cd/m2. Furthermore, using D4CzBNPh-SF as a sensitizer, the TADF-sensitized fluorescence device exhibits a high maximum EQE of 30.7% at a luminance of 575 cd/m2 and a full width at half maximum of 36 nm.
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Unresectable recurrent lymph node metastasis of colorectal cancer (CRC) is considered as an incurable disease clinically and has a very poor prognosis. Here, we report a male KRAS wild-type CRC case with a huge abdominal lymph node metastasis (12 cm in diameter) after CRC surgery. After three intratumoral injections of oncolytic virus (H101) combined with four cycles of low-dose oral capecitabine, the size of the metastatic lymph node shrank remarkably in response to the anticancer drug and a complete response (CR) was achieved with progression-free survival (PFS) of 19 months. The main adverse reaction was mild fever, which was relieved after physical cooling. The patient is in a general good condition now without any relapse of abdominal lymph node for over a year. On this basis, we propose that the combination therapy of oncolytic virus and capecitabine could be a promising clinical therapeutic strategy for unresectable recurrent lymph node metastasis in CRC patients.
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Soil salinization poses a significant global challenge, exerting adverse effects on both agriculture and ecosystems. Planting halophytes has the potential ability to improve saline-alkali land and enhance ecosystem multifunctionality (EMF). However, it remains unclear which halophytes are effective in improving saline-alkali land and what impact they have on the rhizosphere microbial communities and EMF. In this study, we evaluated the Na+ absorption capability of five halophytes (Grubovia dasyphylla, Halogeton glomeratus, Suaeda salsa, Bassia scoparia, and Reaumuria songarica) and assessed their rhizosphere microbial communities and EMF. The results showed that S. salsa possessed the highest shoot (3.13 mmol g-1) and root (0.92 mmol g-1) Na+ content, and its soil Na+ absorption, along with B. scoparia, was significantly higher than that of other plants. The soil pH, salinity, and Na+ content of the halophyte rhizospheres decreased by 6.21%, 23.49%, and 64.29%, respectively, when compared to the bulk soil. Extracellular enzymes in the halophyte rhizosphere soil, including α-glucosidase, ß-glucosidase, ß-1,4-N-acetyl-glucosaminidase, neutral phosphatase, and alkaline phosphatase, increased by 70.1%, 78.4%, 38.5%, 79.1%, and 64.9%, respectively. Furthermore, the halophyte rhizosphere exhibited higher network complexity of bacteria and fungi and EMF than bulk soil. The relative abundance of the dominant phyla Proteobacteria, Firmicutes, and Ascomycota in the halophyte rhizosphere soil increased by 9.4%, 8.3%, and 22.25%, respectively, and showed higher microbial network complexity compared to the bulk soil. Additionally, keystone taxa, including Muricauda, Nocardioides, and Pontibacter, were identified with notable effects on EMF. This study confirmed that euhalophytes are the best choice for saline-alkali land restoration. These findings provided a theoretical basis for the sustainable use of saline-alkali cultivated land.
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Hepatic artery infusion chemotherapy (HAIC) has good clinical efficacy in the treatment of advanced hepatocellular carcinoma (HCC); however, its efficacy varies. This review summarized the ability of various markers to predict the efficacy of HAIC and provided a reference for clinical applications. As of October 25, 2023, 51 articles have been retrieved based on keyword predictions and HAIC. Sixteen eligible articles were selected for inclusion in this study. Comprehensive literature analysis found that methods used to predict the efficacy of HAIC include serological testing, gene testing, and imaging testing. The above indicators and their combined forms showed excellent predictive effects in retrospective studies. This review summarized the strategies currently used to predict the efficacy of HAIC in middle and advanced HCC, analyzed each marker's ability to predict HAIC efficacy, and provided a reference for the clinical application of the prediction system.
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Cyanine dyes are widely used organic probes for in vivo imaging due to their tunable fluorescence. They can form complexes with endogenous albumin, resulting in enhanced brightness and photostability. However, this binding is uncontrollable and irreversible, leading to considerable nonspecific background signals and unregulated circulation time. Methods: Here, we connect varying numbers of 4-(4-iodophenyl) butanoic acid (IP) as albumin-binding moieties (ABM) to the cyanine dye, enabling dynamic and controllable binding with albumin. Meanwhile, we provide a blocking method to completely release the dye from covalent capture with albumin, resulting in specific targeting fluorescence. Furthermore, we evaluate the pharmacokinetics and tumor targeting of the developed dyes. Results: The engineered dyes can dynamically and selectively bind with multiple albumins to change the in situ size of assemblies and circulation time, providing programmable regulation over the imaging time window. The nucleophilic substitution of meso-Cl with water-soluble amino acids or targeting peptides for IP-engineered dye further addresses the nonspecific signals caused by albumin, allowing for adjustable angiography time and efficient tumor targeting. Conclusion: This study rationalizes the binding modes of dyes and proteins, applicable to a wide range of near-infrared (NIR) dyes for improving their in vivo molecular imaging.
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Albuminas , Corantes Fluorescentes , Imagem Óptica , Animais , Corantes Fluorescentes/química , Corantes Fluorescentes/farmacocinética , Albuminas/química , Albuminas/metabolismo , Imagem Óptica/métodos , Neoplasias/diagnóstico por imagem , Camundongos , Humanos , Carbocianinas/química , Camundongos Nus , Linhagem Celular Tumoral , Camundongos Endogâmicos BALB CRESUMO
The primary focus of photopolymerization research is to advance highly efficient visible photoinitiating systems (PISs) as alternatives to conventional ultraviolet (UV) photoinitiators. We developed four multiresonance emitters (BIC-pCz, BNO1, BO-DICz, and TPABO-DICz) to sensitize iodonium salt (Iod) and initiate free-radical and cationic photopolymerization under visible light for the first time. The TPABO-DICz/Iod system achieved a double-bond conversion of over 70% within just 4 s of exposure to green light (520 nm), while the BNO1/Iod system achieved a double-bond conversion exceeding 50% with 10 s of exposure to red light (630 nm). The photochemical properties were studied through thermodynamic research, steady-state photolysis, and electron spin resonance. Photolithography techniques were employed to fabricate photoluminescent films and micrometer-scale patterns utilizing the blue-emitting BIC-pCz dye, showcasing the potential of photolithography in the production of photoluminescent pixels. Additionally, the BIC-pCz/Iod and TPABO-DICz/Iod systems have been employed to rapidly fabricate photoluminescent polymer patterns using a digital-light-processing 3D printer with a low-intensity light (3.2 mW cm-2). These multiresonance emitters show exceptional photosensitizing effects and can act as fluorescent dyes in photoluminescent patterns, highlighting the potential of utilizing photopolymerization for OLED applications.
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In this study, molecularly imprinted polymers (MIPs) were prepared for the specific recognition of organophosphorus pesticides and a rapid, efficient and simple method was established for the detection of dimethoate (DIT) in food samples. Fe3O4 magnetic nanoparticles were synthesized by co-precipitation, and Fe3O4/ZIF-8 complexes were prepared by a modified in-situ polymerization method, and then magnetic molecularly imprinted polymers (MMIPs) were prepared and synthetic route was optimized by applying density functional theory (DFT). The morphological characterization showed that the MMIPs were coarse porous spheres with an average particle size of 50 nm. The synthesized materials are highly selective for the organophosphorus pesticide dimethoate with an adsorption capacity of 461.50 mg·g-1 and are effective resistance to matrix effects. A novel method for the determination of DIT in cabbage was developed using the prepared MMIPs in combination with HPLC. The practical results showed that the method can meet the requirements for the determination of DIT in cabbage with recoveries of 85.6-121.1 % and detection limits of 0.033 µg·kg-1.
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Brassica , Dimetoato , Limite de Detecção , Polímeros Molecularmente Impressos , Dimetoato/análise , Brassica/química , Polímeros Molecularmente Impressos/química , Adsorção , Cromatografia Líquida de Alta Pressão/métodos , Impressão Molecular/métodos , Nanopartículas de Magnetita/química , Extração em Fase Sólida/métodos , Contaminação de Alimentos/análiseRESUMO
There is little research on how Virtual Reality (VR) applications can identify and respond meaningfully to users' emotional changes. In this paper, we investigate the impact of Context-Aware Empathic VR (CAEVR) on the emotional and cognitive aspects of user experience in VR. We developed a real-time emotion prediction model using electroencephalography (EEG), electrodermal activity (EDA), and heart rate variability (HRV) and used this in personalized and generalized models for emotion recognition. We then explored the application of this model in a context-aware empathic (CAE) virtual agent and an emotion-adaptive (EA) VR environment. We found a significant increase in positive emotions, cognitive load, and empathy toward the CAE agent, suggesting the potential of CAEVR environments to refine user-agent interactions. We identify lessons learned from this study and directions for future work.
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Empatia , Realidade Virtual , Gráficos por Computador , Emoções/fisiologia , ConscientizaçãoRESUMO
PURPOSE: Ultrasound is the imaging modality of choice for preoperative diagnosis of lymph node metastasis (LNM) in thyroid cancer (TC), yet its efficacy remains suboptimal. As radiomics gains traction in tumor diagnosis, its integration with ultrasound for LNM differentiation in TC has emerged, but its diagnostic merit is debated. This study assesses the accuracy of ultrasound-integrated radiomics in preoperatively diagnosing LNM in TC. METHODS: Literatures were searched in PubMed, Embase, Cochrane, and Web of Science until July 11, 2023. Quality of the studies was assessed by the radiomics quality score (RQS). A meta-analysis was executed using a bivariate mixed effects model, with a subgroup analysis based on modeling variables (clinical features, radiomics features, or their combination). RESULTS: Among 27 articles (16,410 TC patients, 6356 with LNM), the average RQS was 16.5 (SD:5.47). Sensitivity of the models based on clinical features, radiomics features, and radiomics features plus clinical features were 0.64, 0.76 and 0.69. Specificities were 0.77, 0.78 and 0.82. SROC values were 0.76, 0.84 and 0.81. CONCLUSION: Ultrasound-based radiomics effectively evaluates LNM in TC preoperatively. Adding clinical features does not notably enhance the model's performance. Some radiomics studies showed high bias, possibly due to the absence of standard application guidelines.
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Synthetic near-infrared-II (NIR-II) dyes are promising for deep tissue imaging, yet they are generally difficult to target a given biomolecule with high specificity. Furthermore, the interaction mechanism between albumin and cyanine molecules, which is usually regarded as uncertain "complexes" such as crosslinked nanoparticles, remains poorly understood. Methods: Here, we propose a new class of NIR-II fluorogenic dyes capable of site-specific albumin tagging for in situ albumin seeking/targeting or constructing high-performance cyanine@albumin probes. We further investigate the interaction mechanism between NIR-II fluorogenic dyes and albumin. Results: We identify CO-1080 as an optimal dye structure that produces a stable/bright NIR-II cyanine@albumin probe. CO-1080 exhibits maximum supramolecular binding affinity to albumin while catalyzing their covalent attachment. The probe shows exact binding sites located on Cys476 and Cys101, as identified by proteomic analysis and docking modeling. Conclusion: Our cyanine@albumin probe substantially improves the pharmacokinetics of its free dye counterpart, enabling high-performance NIR-II angiography and lymphography. Importantly, the site-specific labeling tags between NIR-II fluorogenic dyes and albumin occur under mild conditions, offering a specific and straightforward synthesis strategy for NIR-II fluorophores in the fields of targeting bioimaging and imaging-guided surgery.
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Nanopartículas , Proteômica , Corantes Fluorescentes/química , Albuminas , Nanopartículas/química , Imagem Óptica/métodosRESUMO
Despite theoretical difficulties, we herein demonstrate an effective strategy for the inaugural synthesis of an orange-red multiple resonance (MR) emitter centered on a pyridine ring via stereo effects. Compared to conventional benzene-centered materials, the pyridine moiety in the novel MR material acts as a co-acceptor. This results in a significant spectral redshift and a narrower spectrum, as well as an improved photoluminescence quantum yield (PLQY) due to the formation of intramolecular hydrogen bonds. As envisioned, the proof-of-concept emitter Py-Cz-BN exhibits bright orange-red emission peaking at 586 nm with a small full width at half maximum (FWHM) of 0.14 eV (40 nm), exceeding both the wavelength and FWHM achieved with benzene-centered BBCz-Y. Benefiting from high PLQYs (>92%) and suppressed chromophore interactions, the optimized organic light-emitting diodes achieved high maximum external quantum efficiencies of 25.3-29.6%, identical small FWHMs of 0.18 eV (54 nm), and long lifetimes over a wide range of dopant concentrations (1-15 wt%). The performance described above demonstrates the effectiveness of this molecular design and synthesis strategy in constructing high performance long-wavelength MR emitters.
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Cancer represents a global threat to human health, and effective strategies for improved cancer early diagnosis and treatment are urgently needed. The detection of tumor biomarkers has been one of the important auxiliary means for tumor screening and diagnosis. Mitochondria are crucial subcellular organelles that produce most chemical energy used by cells, control metabolic processes, and maintain cell function. Evidence suggests the close involvement of mitochondria with cancer development. As a consequence, the identification of cancer-associated biomarker expression levels in mitochondria holds significant importance in the diagnosis of early-stage diseases and the monitoring of therapy efficacy. Small-molecule fluorescent probes are effective for the identification and visualization of bioactive entities within biological systems, owing to their heightened sensitivity, expeditious non-invasive analysis and real-time detection capacities. The design principles and sensing mechanisms of mitochondrial targeted fluorescent probes are summarized in this review. Additionally, the biomedical applications of these probes for detecting cancer-associated biomarkers are highlighted. The limitations and challenges of fluorescent probes in vivo are also considered and some future perspectives are provided. This review is expected to provide valuable insights for the future development of novel fluorescent probes for clinical imaging, thereby contributing to the advancement of cancer diagnosis and treatment.
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Corantes Fluorescentes , Neoplasias , Humanos , Corantes Fluorescentes/química , Mitocôndrias/metabolismo , Organelas/química , Neoplasias/diagnóstico por imagem , Neoplasias/metabolismo , Biomarcadores/análiseRESUMO
Chiral B/N embedded multi-resonance (MR) emitters open a new paradigm of circularly polarized (CP) organic light-emitting diodes (OLEDs) owing to their unique narrowband spectra. However, pure-red CP-MR emitters and devices remain exclusive in literature. Herein, by introducing a B-N covalent bond to lower the electron-withdrawing ability of the para-positioned B-π-B motif, the first pair of pure-red double hetero-[n]helicenes (n = 6 and 7) CP-MR emitter peaking 617 nm with a small full-width at half-maximum of 38 nm and a high photoluminescence quantum yield of ≈100% in toluene is developed. The intense mirror-image CP light produced by the enantiomers is characterized by high photoluminescence dissymmetry factors (gPL ) of +1.40/-1.41 × 10-3 from their stable helicenes configuration. The corresponding devices using these enantiomers afford impressive CP electroluminescence dissymmetry factors (gEL ) of +1.91/-1.77 × 10-3 , maximum external quantum efficiencies of 36.6%/34.4% and Commission Internationale de I'Éclairage coordinates of (0.67, 0.33), exactly satisfying the red-color requirement specified by National Television Standards Committee (NTSC) standard. Notably a remarkable long LT95 (operational time to 95% of the initial luminance) of ≈400 h at an initial brightness of 10,000 cd m-2 is also observed for the same device, representing the most stable CP-OLED up to date.
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Hepatocellular carcinoma (HCC) is one of the most common malignancies and the third leading cause of cancer-related deaths globally. Hepatic arterial infusion chemotherapy (HAIC) treatment is widely accepted as one of the alternative therapeutic modalities for HCC owing to its local control effect and low systemic toxicity. Nevertheless, although accumulating high-quality evidence has displayed the superior survival advantages of HAIC of oxaliplatin, fluorouracil, and leucovorin (HAIC-FOLFOX) compared with standard first-line treatment in different scenarios, the lack of standardization for HAIC procedure and remained controversy limited the proper and safe performance of HAIC treatment in HCC. Therefore, an expert consensus conference was held on March 2023 in Guangzhou, China to review current practices regarding HAIC treatment in patients with HCC and develop widely accepted statements and recommendations. In this article, the latest evidence of HAIC was systematically summarized and the final 22 expert recommendations were proposed, which incorporate the assessment of candidates for HAIC treatment, procedural technique details, therapeutic outcomes, the HAIC-related complications and corresponding treatments, and therapeutic scheme management.
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Carcinoma Hepatocelular , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/patologia , Neoplasias Hepáticas/patologia , Resultado do Tratamento , Artéria Hepática/patologia , Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Fluoruracila/uso terapêutico , Infusões Intra-ArteriaisRESUMO
BACKGROUND: To compare the efficacy and safety of iodized oil versus polyvinyl alcohol (PVA) particles in portal vein embolization (PVE) before partial hepatectomy. METHODS: From October 2016 to December 2021, 86 patients who planned to undergo hepatectomy after PVE were enrolled, including 61 patients post-PVE with PVA particles + coils and 25 patients post-PVE with iodized oil + coils. All patients underwent CT examination before and 2-3 weeks after PVE to evaluate the future liver remnant (FLR). The intercohort comparison included the degree of liver volume growth, changes in laboratory data, and adverse events. RESULTS: There was no significant difference in the resection rate between the iodized oil group and the PVA particle group (68 % vs. 70 %, p = 0.822). In terms of the degree of hypertrophy (9.52 % ± 13.47 vs. 4.03 % ± 10.55, p = 0.047) and kinetic growth rate (4.07 % ± 5.4 vs. 1.55 % ± 4.63, p = 0.032), the iodized oil group was superior to the PVA group. The PVE operation time in the PVA particle group was shorter than that in the iodized oil group (121. 72 min ± 34.45 vs. 156. 2 min ± 71.58, p = 0.029). There was no significant difference in the degree of hypertrophy between the high bilirubin group and the control group (5.32 % ± 9.21 vs. 6.1 % ± 14.79, p = 0.764). Only 1 patient had a major complication. CONCLUSIONS: Compared with PVA particles, iodized oil PVE can significantly increase liver volume and the degree of hypertrophy without any significant difference in safety.
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Embolização Terapêutica , Neoplasias Hepáticas , Humanos , Hepatectomia/efeitos adversos , Álcool de Polivinil , Óleo Iodado , Veia Porta/cirurgia , Neoplasias Hepáticas/cirurgia , Resultado do Tratamento , Estudos Retrospectivos , Fígado , Embolização Terapêutica/efeitos adversos , Hipertrofia/etiologia , Hipertrofia/cirurgiaRESUMO
Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with narrow emission spectra have garnered significant attention in future organic light-emitting diode (OLED) displays. However, current C=O/N-embedded MR-TADF systems still lack satisfactory performance in terms of electroluminescence bandwidths and external quantum efficiencies (EQEs). In this study, a C=O/N-embedded green MR-TADF emitter, featuring two acridone units incorporated in a sterically protected 11-ring fused core skeleton, is successfully synthesized through finely controlling the reaction selectivity. The superior combination of multiple intramolecular fusion and steric wrapping strategies in the design of the emitter not only imparts an extremely narrow emission spectrum and a high fluorescence quantum yield to the emitter but also mitigates aggregation-induced spectral broadening and fluorescence quenching. Therefore, the emitter exhibits leading green OLED performance among C=O/N-based MR-TADF systems, achieving an EQE of up to 37.2 %, a full width at half maximum of merely 0.11â eV (24â nm), and a Commission Internationale de l'Éclairage coordinate of (0.20, 0.73). This study marks a significant advance in the realization of ideal C=O/N-based MR-TADF emitters and holds profound implications for the design and synthesis of other MR-TADF systems.
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Narrowband emissive multiple resonance (MR) emitters promise high efficiency and stability in deep-blue organic light-emitting diodes (OLEDs). However, the construction of ideal ultra-narrow-band deep-blue MR emitters still faces formidable challenges, especially in balancing bathochromic-shift emission, spectral narrowing, and aggregation suppression. Here, DICz is chosen, which possesses the smallest full-width-at-half-maximum (FWHM) in MR structures, as the core and solved the above issue by tuning its peripheral substitution sites. The 1-substituted molecule Cz-DICz is able to show a bright deep-blue emission with a peak at 457 nm, an extremely small FWHM of 14 nm, and a CIE coordinate of (0.14, 0.08) in solution. The corresponding OLEDs exhibit high maximum external quantum efficiencies of 22.1%-25.6% and identical small FWHMs of 18 nm over the practical mass-production concentration range (1-4 wt.%). To the best of the knowledge, 14 and 18 nm are currently the smallest FWHM values for deep-blue MR emitters with similar emission maxima under photoluminescence and electroluminescence conditions, respectively. These discoveries will help drive the development of high-performance narrowband deep-blue emitters and bring about a revolution in OLED industry.