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Mercury ion (Hg2+), a heavy metal cation with greater toxicity, is widely present in the ecological environment and has become a serious threat to human health and environmental safety. Currently, developing a solution to simultaneously visualize and monitor Hg2+ in environmental samples, including water, soil, and plants, remains a great challenge. In this work, we created and synthesized a near-infrared fluorescent probe, BBN-Hg, and utilized Hg2+ to trigger the partial cleavage of the carbon sulfate ester in BBN-Hg as a sensing mechanism, and the fluorescence intensity of BBN-Hg was significantly enhanced at 650 nm, thus realizing the visualization of Hg2+ with good selectivity (detection limit, 53 nM). In live cells and zebrafish, the probe BBN-Hg enhances the red fluorescence signal in the presence of Hg2+, and successfully performs 3D imaging on zebrafish, making it a powerful tool for detecting Hg2+ in living systems. More importantly, with BBN-Hg, we are able to detect Hg2+ in actual water samples, soil and plant seedling roots. Furthermore, the probe was prepared as a test strip for on-site determination of Hg2+ with the assistance of a smartphone. Therefore, this study offers an easy-to-use and useful method for tracking Hg2+ levels in living organisms and their surroundings.
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Contact Electro-Catalysis (CEC) using commercial dielectric materials in contact-separation cycles with water triggers interfacial electron transfer, generating reactive oxygen species (ROS). However, the hydrophobicity of these materials limits reaction sites, and the generated ROS often combine to form hydrogen peroxide (H2O2), which does not decompose further, leading to suboptimal rates. Addressing H2O2 generation and activation is crucial for advancing CEC. Here, we synthesized a catalyst by loading polytetrafluoroethylene (PTFE) onto ZSM-5 (PZ), achieving uniform dispersion in water. Introducing an FeIII-initiated self-cycling Fenton system (SF-CEC), with synergistic O2 activation and FeIII-activated H2O2, enhanced ROS generation. This system enabled nearly 99% degradation of azo dyes within 10 minutes, a sixfold improvement over traditional CEC. It represents the fastest ultrasound-induced degradation rate of methyl orange dye to date. Without extra oxidants, it also achieved stable dissolution of precious metals in weakly acidic solutions at room temperature, with 80% gold dissolution within 2 hours-2.5 times faster than similar systems. This study corrects the perception of CEC under acidic conditions, offering new insights for dye degradation and precious metal recovery.
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PURPOSE: This study aims to evaluate outcomes in patients with mesenteric artery embolism (MAE) who received primary endovascular therapy (EVT) or laparotomy, and investigate risk factors for 30-day mortality. METHODS: A retrospective analysis of 94 MAE patients who underwent two different treatment strategies was undertaken. An inverse probability of treatment weighting (IPTW) method was used to balance the confounding effects of baseline clinical data. Logistic regression analysis was performed to compare the outcomes according to type of treatment regimens before and after IPTW. Univariate and multivariable analysis were conducted to determine the risk factors for 30-day mortality. RESULTS: Twenty-eight MAE patients received primary EVT, and 66 Open Surgery (OS). Logistic regression analysis showed that there was no significant difference between the EVT and OS group in 30-day mortality rate before (odds ratio [OR] 0.477, 95% confidence interval [CI] 0.170 to 1.340, P = 0.160), and after IPTW (OR 0.647, 95% CI 0.210 to 1.993, P = 0.449). After IPTW, it revealed that the rates of second-look surgery (OR 36.727, 95% CI 5.407 to 249.458, P < 0.001) and hospital stay [> 30 days] (OR 0.006, 95% CI 0.000 to 0.363, P = 0.014) were different in the two groups. D-dimer (> 4 mg/L) and procalcitonin (> 0.5 ng/mL) were the independent risk factors for 30-day mortality in MAE patients postoperatively (P < 0.05). CONCLUSION: In this retrospective study, MAE patients who performed primary EVT had no obvious difference in 30-day mortality rate compared to those who received OS; but it was conducive to reducing prolonged hospital stays. An increase in procalcitonin level and higher D-dimer were associated with short-term poor prognosis in patients with MAE.
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Motor imagery EEG classification plays a crucial role in non-invasive Brain-Computer Interface (BCI) research. However, the performance of classification is affected by the non-stationarity and individual variations of EEG signals. Simply pooling EEG data with different statistical distributions to train a classification model can severely degrade the generalization performance. To address this issue, the existing methods primarily focus on domain adaptation, which requires access to the test data during training. This is unrealistic and impractical in many EEG application scenarios. In this paper, we propose a novel multi-source domain generalization framework called EEG-DG, which leverages multiple source domains with different statistical distributions to build generalizable models on unseen target EEG data. We optimize both the marginal and conditional distributions to ensure the stability of the joint distribution across source domains and extend it to a multi-source domain generalization framework to achieve domain-invariant feature representation, thereby alleviating calibration efforts. Systematic experiments conducted on a simulative dataset, BCI competition IV 2a, 2b, and OpenBMI datasets, demonstrate the superiority and competitive performance of our proposed framework over other state-of-the-art methods. Specifically, EEG-DG achieves average classification accuracies of 81.79% and 87.12% on datasets IV-2a and IV-2b, respectively, and 78.37% and 76.94% for inter-session and inter-subject evaluations on dataset OpenBMI, which even outperforms some domain adaptation methods. Our code is available at https://github.com/zxchit2022/EEG-DG for evaluation.
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Heavy metals, including Hg2+, Cr6+ and Cd2+, have always been a major issue in environmental pollution, leading to abnormal changes in the levels of biologically active molecules including Cys in plants, seriously affecting all aspects of the growth and development of plants. This makes it essential to develop a simple and practical method to study the potential impact of heavy metals on plants. In this paper, our research group has developed near-infrared fluorescent probe WRM-S, which has the advantages of fast response, sensitivity to Cys, and successfully applying it to cells and zebrafish. Moreover, it combined the close relationship between heavy metal stress on plants and Cys, using Cys as the detection target, monitoring the internal environment changes of two plants under Hg2+, Cr6+, and Cd2+ stress in the environment, and then conducting 3D imaging. The results indicated that the probe has strong penetration ability in plant tissues, and revealed abnormal changes in plant Cys levels caused by heavy metal stress-induced cellular oxidative stress or cytotoxicity. Thus, the in-situ imaging detection of this probe provides a direction for the physiological dynamics research of plant environmental stress.
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Cisteína , Colorantes Fluorescentes , Metales Pesados , Raíces de Plantas , Pez Cebra , Colorantes Fluorescentes/química , Cisteína/metabolismo , Cisteína/química , Animales , Raíces de Plantas/metabolismo , Raíces de Plantas/química , Raíces de Plantas/efectos de los fármacos , Arabidopsis/efectos de los fármacos , Arabidopsis/metabolismoRESUMEN
The synthesis of phase-pure carbide nanomaterials is crucial for understanding their structure-performance relationships, and for advancing their application in catalysis. Molybdenum carbides, in particular, have garnered increasing interest due to their Pt-like surface electronic properties and high catalytic activity. Traditional methods for synthesizing molybdenum carbide are often lengthy and energy-intensive, leading to an uncontrolled phase, low purity, and excessive carbon coverage, which hinder their catalytic performance improvement. This work introduces a novel pulsed Joule heating (PJH) technique that overcomes these limitations, enabling the controlled synthesis of high-purity molybdenum carbides (ß-Mo2C, η-MoC1-x, and α-MoC1-x) within seconds by using MoOx/4-Cl-o-phenylenediamine as the hybrid precursor. The PJH method allows precise control over the diffusion of carbon species in the Mo-C system, resulting in a significantly improved phase purity of up to 96.89 wt%. Moreover, the electronic structure of platinum catalysts on molybdenum carbide was modulated through electron metal-support interaction (EMSI) between Pt and MoxC, and contributed to enhanced catalytic performance compared to carbon-supported Pt catalysts during the hydrogen evolution reaction. Overall, this work paves the way for efficient production of high-quality molybdenum carbide nanomaterials, and thus is expected to accelerate their industrial deployments in practical catalytic reactions.
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BACKGROUND: Diffusion-weighted imaging (DWI) has been developed to stage liver fibrosis. However, its diagnostic performance is inconsistent among studies. Therefore, it is worth studying the diagnostic value of various diffusion models for liver fibrosis in one cohort. AIM: To evaluate the clinical potential of six diffusion-weighted models in liver fibrosis staging and compare their diagnostic performances. METHODS: This prospective study enrolled 59 patients suspected of liver disease and scheduled for liver biopsy and 17 healthy participants. All participants underwent multi-b value DWI. The main DWI-derived parameters included Mono-apparent diffusion coefficient (ADC) from mono-exponential DWI, intravoxel incoherent motion model-derived true diffusion coefficient (IVIM-D), diffusion kurtosis imaging-derived apparent diffusivity (DKI-MD), stretched exponential model-derived distributed diffusion coefficient (SEM-DDC), fractional order calculus (FROC) model-derived diffusion coefficient (FROC-D) and FROC model-derived microstructural quantity (FROC-µ), and continuous-time random-walk (CTRW) model-derived anomalous diffusion coefficient (CTRW-D) and CTRW model-derived temporal diffusion heterogeneity index (CTRW-α). The correlations between DWI-derived parameters and fibrosis stages and the parameters' diagnostic efficacy in detecting significant fibrosis (SF) were assessed and compared. RESULTS: CTRW-D (r = -0.356), CTRW-α (r = -0.297), DKI-MD (r = -0.297), FROC-D (r = -0.350), FROC-µ (r = -0.321), IVIM-D (r = -0.251), Mono-ADC (r = -0.362), and SEM-DDC (r = -0.263) were significantly correlated with fibrosis stages. The areas under the ROC curves (AUCs) of the combined index of the six models for distinguishing SF (0.697-0.747) were higher than each of the parameters alone (0.524-0.719). The DWI models' ability to detect SF was similar. The combined index of CTRW model parameters had the highest AUC (0.747). CONCLUSION: The DWI models were similarly valuable in distinguishing SF in patients with liver disease. The combined index of CTRW parameters had the highest AUC.
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Imagen de Difusión por Resonancia Magnética , Hepatopatías , Humanos , Imagen de Difusión por Resonancia Magnética/métodos , Imagen de Difusión Tensora/métodos , Cirrosis Hepática/diagnóstico por imagen , Cirrosis Hepática/patología , Estudios ProspectivosRESUMEN
Palladium hydrides (PdHx) are pivotal in both fundamental research and practical applications across a wide spectrum. PdHx nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature. The substantial challenges in characterizing nanoscale structures contribute to the limited understanding of this anomalous phenomenon. Here, through a series of well-conceived experimental designs and advanced characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), in situ X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), we have uncovered evidence that indicates the presence of C and N within the lattice of Pd (PdCxNy), rather than H (PdHx). By combining theoretical calculations, we have thoroughly studied the potential configurations and thermodynamic stability of PdCxNy, demonstrating a 2.5:1 ratio of C to N infiltration into the Pd lattice. Furthermore, we successfully modulated the electronic structure of Pd nanocrystals through C and N doping, enhancing their catalytic activity in methanol oxidation reactions. This breakthrough provides a new perspective on the structure and composition of Pd-based nanocrystals infused with light elements, paving the way for the development of advanced catalytic materials in the future.
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We investigate the magnetic and transport properties of a kagome magnet YbMn6Sn6. We have grown YbMn6Sn6single crystals having a HfFe6Ge6type structure with ordered Yb and Sn atoms, which is different from the distorted structure previously reported. The single crystal undergoes a ferromagnetic phase transition around 300 K and a ferrimagnetic transition at approximately 30 K, and the magnetic transition at low temperature may be correlated to the ordered Yb sublattice. Negative magnetoresistance has been observed at high temperatures, while the positive magnetoresistance appears at 5 K when the current is oriented out of kagome plane. We observe a large anisotropic anomalous Hall effect with the intrinsic Hall contribution of 141 Ω-1cm-1forσzxintand 32 Ω-1cm-1forσxyint, respectively. These values are similar to those in YMn6Sn6with the same anisotropy. The magnetic transition and anomalous Hall behavior in YbMn6Sn6highlights the influence of the ordered Yb atoms and rare earth elements on its magnetic and transport properties.
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This study proposes a novel inferior vena cava filter (IVCF) design, "Lotus," aiming to enhance release stability and endothelialization. A catheter-filter-vessel model was established for IVCF property analysis, validated by comparing numerical simulations and in vitro tests. Lotus's mechanical properties were analyzed, and optimization suggestions are provided. Compared to existing clinical filters, Lotus demonstrates improved release stability and thrombus capture ability. This work suggests Lotus as a potential technical reference for improved IVCF treatment.
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The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo- and electro- chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact-electro-catalysis, initiating chemical reactions through charge exchange at a solid-liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2â µmol â gcat -1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (â OH) and superoxide radicals (â OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4 under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas-phase catalytic reactions, underscore a significant advance in catalysis.
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BACKGROUND AND PURPOSE: In-stent stenosis is commonly observed after stent implantation. There is no consensus on the contributing factors for in-stent stenosis, especially for aneurysms located at or beyond the circle of Willis in the anterior circulation. This study aimed to investigate the morbidity and determinants of in-stent stenosis in distal anterior circulation aneurysms following the implantation of Pipeline Embolization Devices. MATERIALS AND METHODS: Patients who underwent Pipeline Embolization Device treatment at our center between January 1, 2018, and June 15, 2023, were enrolled. Distal anterior circulation aneurysms were defined as those occurring at or beyond the circle of Willis, including anterior communicating artery aneurysms, anterior cerebral artery aneurysms, and MCA aneurysms. Baseline information, aneurysm characteristics, and follow-up data of patients were analyzed. Patients were divided into 2 groups: the in-stent stenosis group (patients with a loss of >25% of the lumen diameter of the parent artery) and the non-in-stent stenosis group. Binary logistic regression and restricted cubic spline curves were used to explore risk factors. RESULTS: We included 85 cases of 1213 patients treated with flow-diverter devices at our hospital. During an average follow-up period of 9.07 months, the complete occlusion rate was 77.64%. The overall incidence of in-stent stenosis was 36.47% (31/85), of which moderate stenosis accounted for 9.41% (8/85), and severe stenosis, 5.88% (5/85) (triglyceride-glucose index ≥ 8.95; OR = 6.883, P = .006). The difference in diameters between the stent and parent artery of ≥0.09 mm (OR = 6.534, P = .015) and 55 years of age or older (OR = 3.507, P = .036) were risk factors for in-stent stenosis. The restricted cubic spline curves indicated that the risk of in-stent stenosis increased as the difference in diameter between stent and parent artery and the triglyceride-glucose index increased. CONCLUSIONS: Compared with the on-label use of Pipeline Embolization Devices, the rate of in-stent stenosis did not obviously increase when treating distal anterior circulation aneurysms with these devices. The incidence of in-stent stenosis was 36.47% when defined as a lumen diameter loss of >25%, and 15.2% when defined as a lumen diameter loss of >50%. Stent-size selection and biochemical indicators can potentially impact the incidence of in-stent stenosis.
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Charged microdroplets offer novel electrochemical environments, distinct from traditional solid-liquid or solid-liquid-gas interfaces, due to the intense electric fields at liquid-gas interfaces. In this study, we propose that charged microdroplets serve as microelectrochemical cells (MECs), enabling unique electrochemical reactions at the gas-liquid interface. Using electrospray-generated microdroplets, we achieved multielectron CO2 reduction and C-C coupling to synthesize ethanol using molecular catalysts. These catalysts effectively harness and relay electrons, enhancing the longevity of solvated electrons and enabling multielectron reactions. Importantly, we revealed the intrinsic relationship between the size and charge density of a MEC and its reaction selectivity. Employing in situ mass spectrometry, we identified reaction intermediates (molecular catalyst adducts with HCOO) and oxidation products, elucidating the CO2 reduction mechanism and the comprehensive reaction procedure. Our research underscores the promising role of charged microdroplets in pioneering new electrochemical systems.
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Charged microdroplets are favored in microfluidic control, biomedicine, chemistry and materials processing due to their unique physicochemical environment, including interface double layers, high electric fields, surface concentration enrichment, and more. Herein, we investigated the crystallization of charged sodium chloride microdroplets and achieved the formation of hollow single crystals in a single-step process lasting only a few seconds, without the use of templates. Additionally, we discussed the plausible crystal growth mechanism, which appears to be an unconventional outward-inward growth process.
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PURPOSE: Traditional flow diverters (FDs) for treating aneurysms at the fetal posterior communicating artery are unsatisfactory. Surpass Streamline is a novel FD with different mesh characteristics; however, the outcomes for such aneurysms remain unclear. This study aimed to compare hemodynamic alterations induced by Surpass Streamline, Pipeline Flex, and Tubridge devices and explore possible strategies for aneurysms at the fetal posterior communicating artery. METHODS: Two simulated aneurysms (Case 1, Case 2) were constructed from digital subtraction angiography (DSA). The three FDs were virtually deployed, and hemodynamic analysis based on computational fluid dynamics was performed. Hemodynamic parameters, including the sac-averaged velocity magnitude (Velocity), high-flow volume (HFV), and wall shear stress (WSS), were compared between each FD and the untreated model (control). Surpass Streamline was performed in real life for two aneurysms and the clinical outcomes were collected for analysis. RESULTS: Compared to the control, the Surpass resulted in the most significant reduction in flow. In Case 1, the Velocity, HFV, and WSS were reduced by 51.6%, 78.1%, and 64.3%, respectively. In Case 2, the Velocity, HFV, and WSS were reduced by 48.0%, 81.1%, and 65.3%, respectively. Tubridge showed slightly larger changes in hemodynamic parameters than Pipeline. In addition, our analysis suggested that metal coverage was correlated with the WSS, Velocity, and HFV. The postoperative DSA showed that the aneurysm was nearly occluded in Case 1 and decreased in Case 2. CONCLUSION: Compared to that with the Pipeline and Tubridge, the Surpass resulted in the greatest reduction in hemodynamic parameters and might be effective for aneurysms at the fetal posterior communicating artery. Virtual FD deployment and computational fluid dynamics analysis may be used to predict the treatment outcomes.
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Aneurisma Intracraneal , Humanos , Aneurisma Intracraneal/terapia , Aneurisma Intracraneal/cirugía , Hemodinámica , Resultado del Tratamiento , Hidrodinámica , ArteriasRESUMEN
Objective: Schizophrenia is a multifaceted disorder associated with structural brain heterogeneity. Despite its relevance for identifying illness subtypes and informative biomarkers, structural brain heterogeneity in schizophrenia remains incompletely understood. Therefore, the objective of this study was to provide a comprehensive insight into the structural brain heterogeneity associated with schizophrenia. Methods: This meta- and mega-analysis investigated the variability of multimodal structural brain measures of white and gray matter in individuals with schizophrenia versus healthy controls. Using the ENIGMA dataset of MRI-based brain measures from 22 international sites with up to 6139 individuals for a given brain measure, we examined variability in cortical thickness, surface area, folding index, subcortical volume and fractional anisotropy. Results: We found that individuals with schizophrenia are distinguished by higher heterogeneity in the frontotemporal network with regard to multimodal structural measures. Moreover, individuals with schizophrenia showed higher homogeneity of the folding index, especially in the left parahippocampal region. Conclusions: Higher multimodal heterogeneity in frontotemporal regions potentially implies different subtypes of schizophrenia that converge on impaired frontotemporal interaction as a core feature of the disorder. Conversely, more homogeneous folding patterns in the left parahippocampal region might signify a consistent characteristic of schizophrenia shared across subtypes. These findings underscore the importance of structural brain variability in advancing our neurobiological understanding of schizophrenia, and aid in identifying illness subtypes as well as informative biomarkers.
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Inspired by the diversity of biological neurons, quadratic artificial neurons can play an important role in deep learning models. The type of quadratic neurons of our interest replaces the inner-product operation in the conventional neuron with a quadratic function. Despite promising results so far achieved by networks of quadratic neurons, there are important issues not well addressed. Theoretically, the superior expressivity of a quadratic network over either a conventional network or a conventional network via quadratic activation is not fully elucidated, which makes the use of quadratic networks not well grounded. In practice, although a quadratic network can be trained via generic backpropagation, it can be subject to a higher risk of collapse than the conventional counterpart. To address these issues, we first apply the spline theory and a measure from algebraic geometry to give two theorems that demonstrate better model expressivity of a quadratic network than the conventional counterpart with or without quadratic activation. Then, we propose an effective training strategy referred to as referenced linear initialization (ReLinear) to stabilize the training process of a quadratic network, thereby unleashing the full potential in its associated machine learning tasks. Comprehensive experiments on popular datasets are performed to support our findings and confirm the performance of quadratic deep learning. We have shared our code in https://github.com/FengleiFan/ReLinear.
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Effects of continuous cropping on rhizosphere soil physical and chemical properties, soil microbial activity, and community characteristics of Codonopsis pilosula were investigated. The C. pilosula plot(CK) fallow for five years and C. pilosula fields with different years of continuous cropping were studied using Illumina high-throughput sequencing technology combined with soil physical and chemical properties analysis. The response of rhizosphere soil physical and chemical properties, microbial activities, and microbial community characteristics to continuous cropping years of C. pilosula were investigated. The results were as follows:the contents of organic carbon, total phosphorus, total nitrogen, and salt in rhizosphere soil of C. pilosula increased with the extension of continuous cropping years. However, soil pH value decreased with the extension of continuous cropping years. Compared with that in the CK treatment, rhizosphere soil organic carbon content of C. pilosula in continuous cropping for one, two, three, and four years increased by 11.1%, 80.5%, 74.9%, and 78.2%, respectively. Total phosphorus content increased by 11.8%, 52.9%, 66.7%, and 78.4%, and total nitrogen content increased by 31.3%, 68.8%, 52.1%, and 56.3%, respectively. Soil salt content increased significantly under continuous cropping of three and four years, and soil conductivity increased by 54.2% and 84.7% compared with that in the CK treatment, respectively. The C/N ratio of microbial biomass in rhizosphere soil exhibited an increasing trend with the extension of continuous cropping years. Soil respiration entropy and microbial entropy showed a decreasing trend. With the increase in continuous cropping years, the diversity and abundance of bacteria in soil decreased, whereas the diversity and abundance of fungi increased. In addition, with the increase in continuous cropping years, the antagonistic effect between bacterial communities was enhanced, whereas the synergistic effect between fungal communities was mainly observed. Correlation analysis showed that soil total phosphorus, available potassium, carbon to nitrogen ratio of microbial biomass, soil respiration entropy, microbial biomass carbon, and electrical conductivity were the main factors affecting the changes in soil bacterial community characteristics. Soil total nitrogen, available potassium, available phosphorus, and soil respiration entropy were the main factors affecting the changes in fungal community characteristics. In conclusion, continuous cropping significantly changed the physical and chemical properties of soil and microbial activity and affected the abundance and diversity of bacteria and fungi in soil. This changed the interaction between microorganisms, which disrupted the stability of microbial communities in the soil.
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Codonopsis , Suelo , Suelo/química , Carbono , Rizosfera , Microbiología del Suelo , Hongos , Bacterias/genética , Nitrógeno , Fósforo , PotasioRESUMEN
The excited state properties and deactivation pathways of two DNA methylation inhibitors, i.e., 5-azacytidine (5ACyd) and 2'-deoxy-5-azacytidine (5AdCyd) in aqueous solution, are comprehensively explored with the QM(CASPT2//CASSCF)/MM protocol. We systematically map the feasible decay mechanisms based on the obtained excited-state decay paths involving all the identified minimum-energy structures, conical intersections, and crossing points driving the different internal conversion (IC) and intersystem crossing (ISC) routes in and between the 1ππ*, 1nπ*, 3ππ*, 3nπ*, and S0 states. Unlike the 1nπ* state below the 1ππ* state in 5ACyd, deoxyribose group substitution at the N1 position leads to the 1ππ* state becoming the S1 state in 5AdCyd. In 5ACyd and 5AdCyd, the initially populated 1ππ* state mainly deactivates to the S0 state through the direct 1ππ* â S0 IC or mediated by the 1nπ* state. The former nearly barrierless IC channel of 1ππ* â S0 occurs ultrafast via the nearby low-lying 1ππ*/S0 conical intersection. In the latter IC channel of 1ππ* â 1nπ* â S0, the initially photoexcited 1ππ* state first approaches the nearby S2/S1 conical section 1ππ*/1nπ* and then undergoes efficient IC to the 1nπ* state, followed by the further IC to the initial S0 state via the S1/S0 conical intersection 1nπ*/S0. The 1nπ*/S0 conical intersection is estimated to be located 6.0 and 4.9 kcal mol-1 above the 1nπ* state minimum in 5ACyd and 5AdCyd, respectively, at the QM(CASPT2)/MM level. In addition to the efficient singlet-mediated IC channels, the minor ISC routes would populate 1ππ* to T1(ππ*) through 1ππ* â T1 or 1ππ* â 1nπ* â T1. Relatively, the 1ππ* â 1nπ* â T1 route benefits from the spin-orbit coupling (SOC) of 1nπ*/3ππ* of 8.7 cm-1 in 5ACyd and 10.2 cm-1 in 5AdCyd, respectively. Subsequently, the T1 system will approach the nearby T1/S0 crossing point 3ππ*/S0 driving it back to the S0 state. Given the 3ππ*/S0 crossing point located above the T1 minimum and the small T1/S0 SOC, i.e., 8.4 kcal mol-1 and 2.1 cm-1 in 5ACyd and 6.8 kcal mol-1 and 1.9 cm-1 in 5AdCyd, respectively, the slow T1 â S0 would trap the system in the T1 state for a while. The present work could contribute to understanding the mechanistic photophysics and photochemistry of similar aza-nucleosides and their derivatives.
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Background: Erdheim-Chester disease is a form of histiocytosis. It is an extremely rare illness. Since its discovery, hundreds of cases of this disease have been identified across the globe. Pathologically, the condition is characterized by proliferation of lipid-rich foam-like tissue cells, which is especially prevalent in bones. Approximately 50% of patients develop infiltration into organs other than the bones. Case description: A patient with fever and bone pain is described in this case report. After visiting multiple hospitals and departments, undergoning battery of investigations, and ruling out other diseases, the patient was pathologically diagnosed with Erdheim-Chester disease after a biopsy of the associated bone destruction. The condition improved with symptomatic therapy. Conclusion: Numerous clinical symptoms make non-Langerhans cell histiocytosis challenging to diagnose and requires pathological diagnosis. Patients with unexplained multiple bone destruction must be alert against this disease from a clinical standpoint.