RESUMO
Carbazole-based self-assembled molecules (SAMs) are widely applied in inverted perovskite solar cells (iPSCs) due to their unique molecular properties. However, the symmetrical structure of the carbazole-based SAMs makes it difficult to finely regulate their performance, which impedes the further enhancement of the efficiency and stability of iPSCs. This work shows that by building an asymmetric carbazole core, the crucial properties of SAM molecules can be effectively regulated. It has been confirmed that the hybrid thieno[2,3-b]thiophene unit of this asymmetric core governs the energy level, the surface wettability, and the defect passivation capability of the SAMs, while the substituent of core has a greater impact on the molecular dipole and device stability. The synergistic effects from thieno[2,3-b]thiophene and fluorine lead to the KF-derived iPSC demonstrating a certified power conversion efficiency (PCE) of 25.17% and excellent operational stability. This hybrid design concept offers a promising approach for the further structural modification of SAMs in iPSCs.
RESUMO
Crystallization of organic materials can lead to different assembly structure with different reactivity, but this phenomenon is rarely observed for delocalized hydrocarbon radicals. This report introduces a crystallization-induced radical-radical coupling reaction, which employs a series of stable nonplanar organic π-radicals as reactants. Six stable radical congeners are synthesized, resulting in radical-radical coupling at the allenyl radical site during crystallization to produce close-shell dimers. This coupling reaction is absent in the solution phase, which highlights the importance of preorganization in the lattice. Remarkably, the attempts of cocrystallization of different congeners yielded homocoupling products instead of cross-coupling products. In specific cases, two distinct polymorphs are observed and their reactivity is different according to the distance of the reaction sites. Theoretical calculations indicate that the transition from a metastable preorganized monomer to a dimer is barrierless and spontaneous. The dimer could regenerate free radicals by heating or photoirradiation in the solution phase. This discovery may lead to controllable molecular switches.
RESUMO
Near-infrared (NIR) circularly polarized absorbing or emitting materials offer distinct advantages over their visible-light counterparts and have attracted considerable interest across various fields. Materials exhibiting NIR chiroptical properties with high fluorescence quantum yields (ΦF) are particularly rare. In this study, we report the synthesis of a series of helical nanographenes (1, 2, 3, and 4), where perylene is fused with one to four hexa-peri-hexabenzocoronene (sub)units via a strategy involving Diels-Alder cycloaddition followed by Scholl reaction. X-ray crystallographic analysis confirmed their structures, revealing helicene moieties integrated into a highly contorted framework. Benefiting from a similar distribution pattern of frontier molecular orbitals to perylene and extended π-conjugation, compounds 1-4 demonstrate respectable ΦF values of 31.9%, 15.0%, 13.7%, and 6.5%, respectively, with emission maxima reaching up to 1010 nm. Their enantiopure forms, isolated by preparative chiral HPLC, exhibit distinct circular dichroism signals and circularly polarized luminescence across a broad spectral range, extending from the ultraviolet to the NIR.
RESUMO
Shallow ditches, which generally receive livestock or domestic sewage, are widely distributed in rural and suburban areas, making them important sites for antibiotic exposure. Because of the easy penetration of solar irradiation, the photochemical reactions of antibiotics tend to be active in shallow ditches. This study investigated the photodegradation potential of 21 commonly used antibiotics belonging to five categories in a typical shallow ditch by conducting simulated solar irradiation experiments. The influence of dissolved organic matter (DOM) in ditch water on the photodegradation of antibiotics was analyzed, and a model based on DOM changes was established to predict the degradation behavior of antibiotics. The results indicated that the degradation rates of different varieties of antibiotics in ultrapure water and ditch water followed the trend of fluoroquinolones > tetracyclines > sulfonamides > macrolides > lincosamides. In ditch water, direct photodegradation and photooxidation mediated by 3DOM∗ played predominant roles in the antibiotic photodegradation, whereas the contributions of singlet oxygen (1O2) and hydroxyl radicals (·OH) vary significantly depending on the reactivity of the antibiotics. A simple and effective model was proposed for predicting the photodegradation process of antibiotics in ditch water based on the degree of DOM photobleaching determined by excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis. The prediction model was simplified by considering the similarity in photochemical properties within the same category of antibiotics and was validated by field tests. This study fills a critical research gap by evaluating the photodegradation of antibiotics in shallow ditches, thereby providing valuable insights into their fate and transport in shallow ditch water.
RESUMO
BACKGROUND: Infraorbital neuralgia is a refractory facial pain that may cause various psychological disorders. There is no optimal treatment for infraorbital neuralgia because few relevant studies have been conducted. Pulsed radiofrequency (PRF) is a minimally invasive procedure that has been proven effective in treating trigeminal neuralgia and other painful diseases. Our previous study demonstrated that high-voltage PRF was effective in patients with infraorbital neuralgia. However, there is little literature on the long-term follow-up of infraorbital neuralgia treated with high-voltage PRF with a large sample size. OBJECTIVES: To explore the long-term effectiveness and safety of high-voltage PRF guided by computed tomography for patients with infraorbital neuralgia who failed conservative treatment. STUDY DESIGN: Monocentric, retrospective, observational study. SETTING: This study enrolled patients with infraorbital neuralgia who failed conservative treatment for infraorbital neuralgia and who underwent a high-voltage PRF procedure at the Department of Pain Management in Beiging Tiantan Hospital. METHODS: From January 2013 through June 2022, a total of 223 patients were included in this study; 16 were excluded according to the exclusion criteria. Finally, the medical records of 207 patients were extracted and analyzed including demographic data, intraoperative records, pain-related baseline, data and side effects. Treatment efficacy was evaluated using the Barrow Neurological Institute scores for pain. The Barrow Neurological Institute pain intensity score, onset time, perioperative complications and the time of recurrence were routinely followed up at month one, month 3, month 6 and every year postoperatively. Recurrence-free survival curves were presented by a Kaplan-Meier plot. RESULTS: The initial pain relief rate after the high-voltage PRF treatment was 86.0%. The cumulative recurrence-free survival rates were 85.5% (at month one), 82.6% (at month 3), 77.8% (at month 6), 65.7%(at month 12), 61.7% (at month 24), 55.8% (at month 48), 47.6% (at month 96) and 45.2% (at month 120) postoperatively. The median follow-up time of the 207 patients was 67.0 months (interquartile range, 38.0-93.0 months; range from 12 months to 125 months), with a median recurrence-free time of 80 months according to the Kaplan-Meier estimator. LIMITATIONS: This was a retrospective observational study. Multicenter, prospective, randomized controlled studies should be conducted. In addition, the optimal parameters for PRF treatment of infraorbital neuralgia need to be further explored. CONCLUSION: Computed tomography-guided high-voltage PRF treatment provides a minimally invasive and effective treatment option for patients with infraorbital neuralgia who fail conservative treatment, which could be considered as a preferred treatment before more invasive treatments.
Assuntos
Tratamento por Radiofrequência Pulsada , Humanos , Estudos Retrospectivos , Tratamento por Radiofrequência Pulsada/métodos , Seguimentos , Masculino , Feminino , Pessoa de Meia-Idade , Idoso , Resultado do Tratamento , Adulto , Neuralgia do Trigêmeo/terapia , Neuralgia do Trigêmeo/cirurgiaRESUMO
Solvent additives with a high boiling point (BP) and low vapor pressure (VP) have formed a key handle for improving the performance of organic solar cells (OSCs). However, it is not always clear whether they remain in the active-layer film after deposition, which can negatively affect the reproducibility and stability of OSCs. In this study, an easily removable solvent additive (4-chloro-2-fluoroiodobenzene (CFIB)) with a low BP and high VP is introduced, behaving like volatile solid additives that can be completely removed during the device fabrication process. In-depth studies of CFIB addition into the D18-Cl donor and N3 acceptor validate its dominant non-covalent intermolecular interactions with N3 through effective electrostatic interactions. Such phenomena improve charge dynamics and kinetics by optimizing the morphology, leading to enhanced performance of D18-Cl:N3-based devices with a power conversion efficiency of 18.54%. The CFIB-treated device exhibits exceptional thermal stability (T80 lifetime = 120 h) at 85 °C compared with the CFIB-free device, because of its morphological robustness by evolving no residual CFIB in the film. The CFIB features a combination of advantages of solvent (easy application) and solid (high volatility) additives, demonstrating its great potential use in the commercial mass production of OSCs.
RESUMO
BACKGROUND AND OBJECTIVE: The accurate diagnosis of schizophrenia spectrum disorder plays an important role in improving patient outcomes, enabling timely interventions, and optimizing treatment plans. Functional connectivity analysis, utilizing functional magnetic resonance imaging data, has been demonstrated to offer invaluable biomarkers conducive to clinical diagnosis. However, previous studies mainly focus on traditional machine learning methods or hand-crafted neural networks, which may not fully capture the spatial topological relationship between brain regions. METHODS: This paper proposes an evolutionary algorithm (EA) based graph neural architecture search (GNAS) method. EA-GNAS has the ability to search for high-performance graph neural networks for schizophrenia spectrum disorder prediction. Moreover, we adopt GNNExplainer to investigate the explainability of the acquired architectures, ensuring that the model's predictions are both accurate and comprehensible. RESULTS: The results suggest that the graph neural network model, derived using genetic algorithm search, outperforms under five-fold cross-validation, achieving a fitness of 0.1850. Relative to conventional machine learning and other deep learning approaches, the proposed method yields superior accuracy, F1 score, and AUC values of 0.8246, 0.8438, and 0.8258, respectively. CONCLUSION: Based on a multi-site dataset from schizophrenia spectrum disorder patients, the findings reveal an enhancement over prior methods, advancing our comprehension of brain function and potentially offering a biomarker for diagnosing schizophrenia spectrum disorder.
RESUMO
Hepatic gluconeogenesis plays a crucial role in maintaining glucose homeostasis and serves as a potential therapeutic target for type 2 diabetes, while its underlying mechanisms are not fully understood. This study elucidates the role of the deubiquitinase OTU domain-containing ubiquitin aldehyde binding protein 1 (OTUB1) in gluconeogenesis. We found that hepatic OTUB1 expression is reduced in both db/db mice and patients with type 2 diabetes. Deletion of hepatic OTUB1 significantly elevates fasting blood glucose levels and increases the expression of key gluconeogenic genes. Conversely, overexpression of OTUB1 in hepatocytes mitigates diabetic hyperglycemia and enhances insulin sensitivity. It is known that the tyrosine 3-monooxygenase/tryptophan 5-monooxygenase activation protein ß (YWHAB) functions as an inhibitor of hepatic gluconeogenesis by interacting with forkhead box protein O (FOXO1) and glucagon receptor (GPCR), but its own modification mechanism remains unclear. Our findings indicate that OTUB1 interacts with YWHAB and deubiquitinates it through a catalytic process, which in turn suppresses gluconeogenesis. Therefore, OTUB1 plays a pivotal role in inhibiting hepatic gluconeogenesis, highlighting its potential as a therapeutic target for type 2 diabetes.
RESUMO
OBJECTIVE: To describe the changes in sleep pattern throughout pregnancy and to evaluate the relationship between sleep and adverse perinatal outcomes. METHODS: Pregnant women at Qianfoshan Hospital completed questionnaires regarding their sleep during each of the three trimesters. Additionally, a subset of participants engaged in objective sleep monitoring using actigraphy devices. In the perinatal period, the following data were collected: pregnancy complications; gestational age; mode of delivery; Apgar scores for the neonate; and birth weight. RESULTS: The total night sleep time in the second trimester was about 15 minutes shorter than that in the first trimester (P=0.024), and about 31 minutes shorter in the third trimester than in the second trimester (P<0.001). The sleep efficiency in the second trimester was about 10.23% lower than in the first trimester (P<0.001), and the efficiency in the third trimester was about 5.16% lower than in the second trimester (P<0.001). The occurrence of pregnancy-induced hypertension (PIH) was associated with sleep duration (P=0.019), sleep efficiency (P<0.001) and PSQI scores (P<0.001) in the first trimester. Furthermore, the mode of delivery was also found to be associated with sleep duration (P=0.011), sleep efficiency (P<0.001) and PSQI scores (P<0.001) in the first trimester. CONCLUSION: With the development of the pregnancy process, the sleep situation gets worse. Pregnant women's sleep situation in the first trimester of pregnancy is associated with the occurrence of PIH and delivery mode.
RESUMO
Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical 1 using a protection-oxidation-protection strategy. Diradical 1 demonstrated exceptional stability, with a solution half-life time exceeding 3.5 years and a solid state thermal decomposition temperature above 300 °C. X-ray crystallographic analysis revealed its intersected molecular structure and tightly bound dimer configuration. A singlet ground state with a small singlet-triplet energy gap is consistently identified using electron paramagnetic resonance (EPR) and a superconducting quantum interference device (SQUID) in a rigid matrix, and the triplet state is thermally accessible at room temperature. The solution phase properties were systematically examined through EPR, absorption spectroscopy, and cyclic voltammetry, revealing a rotational motion in the slow-motion regime and multistage redox characteristics. This study presents an efficient synthetic and stabilization strategy for organic diradicals, enabling the development of various high-spin functional materials.
RESUMO
A three-dimensional (3D) hierarchical microfiber bundle-based scaffold integrated with silver nanowires (AgNWs) and porous polyurethane (PU) was designed for the Joule heater via a facile dip-coating method. The interconnected micrometer-sized voids and unique hierarchical structure benefit uniform AgNWs anchored and the formation of a high-efficiency 3D conductive network. As expected, this composite exhibits a superior electrical conductivity of 1586.4 S/m and the best electrothermal conversion performance of 118.6 °C at 2.0 V compared to reported wearable Joule heaters to date. Moreover, the durable microfiber bundle-PU network provides strong mechanical properties, allowing for the stable and durable electrothermal performance of such a composite to resist twisting, bending, abrasion, and washing. Application studies show that this kind of Joule heater is suitable for a wide range of applications, such as seat heating, a heating jacket, personal thermal management, etc.
RESUMO
Depleting fossil energy sources and conventional polluting power generation pose a threat to sustainable development. Hydroelectricity generation from ubiquitous and spontaneous phase transitions between liquid and gaseous water has been considered a promising strategy for mitigating the energy crisis. Fibrous materials with unique flexibility, processability, multifunctionality, and practicability have been widely applied for fibrous materials-based hydroelectricity generation (FHG). In this review, the power generation mechanisms, design principles, and electricity enhancement factors of FHG are first introduced. Then, the fabrication strategies and characteristics of varied constructions including 1D fiber, 1D yarn, 2D fabric, 2D membrane, 3D fibrous framework, and 3D fibrous gel are demonstrated. Afterward, the advanced functions of FHG during water harvesting, proton dissociation, ion separation, and charge accumulation processes are analyzed in detail. Moreover, the potential applications including power supply, energy storage, electrical sensor, and information expression are also discussed. Finally, some existing challenges are considered and prospects for future development are sincerely proposed.
RESUMO
The assessment of the cognitive workload experienced by air traffic controllers is a complex and prominent issue in the research community. This study introduces new indicators related to gamma waves to detect controllers' workload and develops experimental protocols to capture their EEG data and NASA-TXL data. Then, statistical tests, including the Shapiro-Wilk test and ANOVA, were used to verify whether there was a significant difference between the workload data of the controllers in different scenarios. Furthermore, the Support Vector Machine (SVM) classifier was employed to assess the detection accuracy of these indicators across four categorizations. According to the outcomes, hypotheses suggesting a strong correlation between gamma waves and an air traffic controller's workload were put forward and subsequently verified; meanwhile, compared with traditional indicators, the indicators associated with gamma waves proposed in this paper have higher accuracy. In addition, to explore the applicability of the indicator, sensitive channels were selected based on the mRMR algorithm for the indicator with the highest accuracy, ß + θ + α + γ, showcasing a recognition rate of a single channel exceeding 95% of the full channel, which meets the requirements of convenience and accuracy in practical applications. In conclusion, this study demonstrates that utilizing EEG gamma wave-associated indicators can offer valuable insights into analyzing workload levels among air traffic controllers.
Assuntos
Algoritmos , Aviação , Eletroencefalografia , Carga de Trabalho , Humanos , Eletroencefalografia/métodos , Máquina de Vetores de Suporte , Processamento de Sinais Assistido por Computador , Masculino , AdultoRESUMO
Background: Colorectal cancer (CRC), a prevalent gastrointestinal malignant disease, causes substantial morbidity and mortality. Identification of novel prognostic biomarkers and therapeutic targets is critically needed to improve patient outcomes. Although solute carrier family 12 member 8 (SLC12A8) has high expression in various tumors and affects tumor progression, its role in CRC remains unclear. The aim of this study was to investigate the functions of SLC12A8 in CRC. Methods: SLC12A8 expression and its association with clinical significance in CRC patients were explored via multiple public databases, including The Cancer Genome Atlas (TCGA), Genotype-Tissue Expression (GTEx), The Human Protein Atlas (HPA), The University of ALabama at Birmingham CANcer data analysis Portal (UALCAN), and Kaplan-Meier plotter. The effects of SLC12A8 on the CRC cell apoptosis, epithelial-mesenchymal transition (EMT), reactive oxygen species (ROS) production, and sensitivity to oxaliplatin were verified by in vitro experiments. Results: SLC12A8 expression was upregulated in CRC tissues compared with normal colorectal tissues. Furthermore, high expression of SLC12A8 was associated with poorer prognosis in CRC patients. Pathway enrichment analyses revealed SLC12A8 involvement in oxidative stress and transforming growth factor-beta (TGF-ß) signaling. Experiments in CRC cells showed that SLC12A8 upregulation promoted apoptosis resistance, EMT, and inhibited ROS production. Moreover, SLC12A8 knockdown enhanced the sensitivity of CRC cells to oxaliplatin chemotherapy. Conclusions: Our integrative analyses identify SLC12A8 as a candidate biomarker for CRC progression. Targeting SLC12A8 may improve patient responses to oxaliplatin-based treatment regimens.
RESUMO
Self-supervised contrastive learning draws on power representational models to acquire generic semantic features from unlabeled data, and the key to training such models lies in how accurately to track motion features. Previous video contrastive learning methods have extensively used spatially or temporally augmentation as similar instances, resulting in models that are more likely to learn static backgrounds than motion features. To alleviate the background shortcuts, in this paper, we propose a cross-view motion consistent (CVMC) self-supervised video inter-intra contrastive model to focus on the learning of local details and long-term temporal relationships. Specifically, we first extract the dynamic features of consecutive video snippets and then align these features based on multi-view motion consistency. Meanwhile, we compare the optimized dynamic features for instance comparison of different videos and local spatial fine-grained with temporal order in the same video, respectively. Ultimately, the joint optimization of spatio-temporal alignment and motion discrimination effectively fills the challenges of the missing components of instance recognition, spatial compactness, and temporal perception in self-supervised learning. Experimental results show that our proposed self-supervised model can effectively learn visual representation information and achieve highly competitive performance compared to other state-of-the-art methods in both action recognition and video retrieval tasks.
Assuntos
Gravação em Vídeo , Humanos , Redes Neurais de Computação , Percepção de Movimento/fisiologia , Aprendizado de Máquina Supervisionado , Movimento (Física) , AlgoritmosRESUMO
Platinum-based catalysts exhibit outstanding electrocatalytic performance in the hydrogen evolution reaction (HER). However, platinum-based catalysts face significant challenges due to their rarity and high cost. This paper endeavors to shed light on a promising alternative: polyoxometalate (POM)-based catalysts, which possess significant potential for the synthesis of non-noble metal-based catalysts for the HER. Utilizing POMs as raw materials to assemble POM-derived materials, including POM-derived crystalline materials, metal sulfides, phosphides, carbides, nitrides, and so on, has emerged as an effective approach for the synthesis of hydrogen evolution electrocatalysts. This approach offers advantages in both stability and electrocatalytic performance. This comprehensive review navigates through latest progress in the assembly strategy and HER performance of POM-based crystal materials, alongside discussion on transition metal compounds derived from POMs, such as carbides, phosphides, and sulfides. Besides, future developments in POM-derived electrocatalyst regulation of the electrochemical HER are prospected.
RESUMO
Introduction: Yeast culture (YC) enhances ruminant performance, but its functional mechanism remains unclear because of the complex composition of YC and the uncertain substances affecting rumen fermentation. The objective of this study was to determine the composition of effective metabolites in YC by exploring its effects on rumen fermentation in vitro, growth and slaughter performance, serum index, rumen fermentation parameters, rumen microorganisms, and metabolites in lambs. Methods: In Trial 1, various YCs were successfully produced, providing raw materials for identifying effective metabolites. The experiment was divided into 5 treatment groups with 5 replicates in each group: the control group (basal diet without additives) and YC groups were supplemented with 0.625 of four different yeast cultures, respectively (groups A, B, C, and D). Rumen fermentation parameters were determined at 3, 6, 12, and 24 h in vitro. A univariate regression model multiple factor associative effects index (MFAEI; y) was established to correlate the most influential factors on in vitro rumen fermentation with YC metabolites (x). This identified the metabolites promoting rumen fermentation and optimal YC substance levels. In Trial 2, metabolites in YC not positively correlated with MFAEI were excluded, and effective substances were combined with pure chemicals (M group). This experiment validated the effectiveness of YC metabolites in lamb production based on their impact on growth, slaughter performance, serum indices, rumen parameters, microorganisms, and metabolites. Thirty cross-generation rams (Small tail Han-yang â × Australian white sheep â) with good body condition and similar body weight were divided into three treatment groups with 10 replicates in each group: control group, YC group, pure chemicals combination group (M group). Results: Growth performance and serum index were measured on days 30 and 60, and slaughter performance, rumen fermentation parameters, microorganisms, and metabolites were measured on day 60. The M group significantly increased the dressing percentage, and significantly decreased the GR values of lambs (p < 0.05). The concentration of growth hormone (GH), Cortisol, insulin (INS), and rumen VFA in the M group significantly increased (p < 0.05). Discussion: These experiments confirmed that YC or its screened effective metabolites positively impact lamb slaughter performance, rumen fermentation, and microbial metabolism.
RESUMO
The kink structure in band dispersion usually refers to a certain electron-boson interaction, which is crucial in understanding the pairing in unconventional superconductors. Here we report the evidence of the observation of a kink structure in Fe-based superconductor CsCa2Fe4As4F2 using angle-resolved photoemission spectroscopy. The kink shows an orbital selective and momentum dependent behavior, which is located at 15 meV below Fermi level along the Γ - M direction at the band with dxz orbital character and vanishes when approaching the Γ - X direction, correlated with a slight decrease of the superconducting gap. Most importantly, this kink structure disappears when the superconducting gap closes, indicating that the corresponding bosonic mode (~ 9 ± 1 meV) is closely related to superconductivity. However, the origin of this mode remains unidentified, since it cannot be related to phonons or the spin resonance mode (~15 meV) observed by inelastic neutron scattering. The behavior of this mode is rather unique and challenges our present understanding of the superconducting paring mechanism of the bilayer FeAs-based superconductors.
RESUMO
Excitonic insulators are long-sought-after quantum materials predicted to spontaneously open a gap by the Bose condensation of bound electron-hole pairs, namely, excitons, in their ground state. Since the theoretical conjecture, extensive efforts have been devoted to pursuing excitonic insulator platforms for exploring macroscopic quantum phenomena in real materials. Reliable evidence of excitonic character has been obtained in layered chalcogenides as promising candidates. However, owing to the interference of intrinsic lattice instabilities, it is still debatable whether those features, such as the charge density wave and gap opening, are primarily driven by the excitonic effect or by the lattice transition. Herein, we develop an intercalation chemistry strategy for obtaining a novel charge-transfer excitonic insulator in organic-inorganic superlattice interfaces that serves as an ideal platform to decouple the excitonic effect from the lattice effect. In this system, we observe a narrow excitonic gap, formation of a charge density wave without periodic lattice distortion, and metal-insulator transition, providing visualized evidence of exciton condensation occurring in thermal equilibrium. Our findings identify self-assembly intercalation chemistry as a new strategy for developing novel excitonic insulators.