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A mobility edge (ME), representing the critical energy that distinguishes between extended and localized states, is a key concept in understanding the transition between extended (metallic) and localized (insulating) states in disordered and quasiperiodic systems. Here we explore the impact of dissipation on a quasiperiodic system featuring MEs by calculating steady-state density matrix and analyzing quench dynamics with sudden introduction of dissipation. We demonstrate that dissipation can lead the system into specific states predominantly characterized by either extended or localized states, irrespective of the initial state. Our results establish the use of dissipation as a new avenue for inducing transitions between extended and localized states and for manipulating dynamic behaviors of particles.
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BACKGROUND: We aimed to identify preoperative predictors of aggressive pathology for cT1 solid renal cell carcinoma (RCC) by combining clinical features with qualitative and quantitative CT parameters, and developed a nomogram model. METHODS: We conducted a retrospective study of 776 cT1 solid RCC patients treated with partial nephrectomy (PN) or radical nephrectomy (RN) between 2018 and 2022. All patients underwent four-phase contrast-enhanced CT scans and the CT parameters were obtained by two experienced radiologists using region of interest (ROI). Aggressive pathology was defined as patients with nuclear grade III-IV; upstage to pT3a; type II papillary renal cell carcinoma (pRCC), collecting duct or renal medullary carcinoma, unclassified RCC or sarcomatoid/rhabdoid features. Univariate and multivariate logistic analyses were used to determine significant predictors and develop the nomogram model. To evaluate the accuracy and clinical utility of the nomogram model, we used the receiver operating characteristic (ROC) curve, calibration plot, decision curve analysis (DCA), risk stratification, and subgroup analysis. RESULTS: Of the 776 cT1 solid RCC patients, 250 (32.2%) had aggressive pathological features. The interclass correlation coefficient (ICC) of CT parameters accessed by two reviewers ranged from 0.758 to 0.982. Logistic regression analyses showed that neutrophil-to-lymphocyte ratio (NLR), distance to the collecting system, CT necrosis, tumor margin irregularity, peritumoral neovascularity, and RER-NP were independent predictive factors associated with aggressive pathology. We built the nomogram model using these significant variables, which had an area under the curve (AUC) of 0.854 in the ROC curve. CONCLUSIONS: Our research demonstrated that preoperative four-phase contrast-enhanced CT was critical for predicting aggressive pathology in cT1 solid RCC, and the constructed nomogram was useful in guiding patient treatment and postoperative follow-up.
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Carcinoma de Células Renais , Neoplasias Renais , Humanos , Carcinoma de Células Renais/diagnóstico por imagem , Carcinoma de Células Renais/cirurgia , Carcinoma de Células Renais/patologia , Nomogramas , Estudos Retrospectivos , Neoplasias Renais/diagnóstico por imagem , Neoplasias Renais/cirurgia , Neoplasias Renais/patologia , Tomografia Computadorizada por Raios XRESUMO
Vibrio parahaemolyticus (V. parahaemolyticus) is a major foodborne pathogen, which can cause serious foodborne illnesses like diarrhoea. Rapid on-site detection of foodborne pathogens is an ideal way to respond to foodborne illnesses. Herein, we provide an electrochemical sensor for rapid on-site detection. This sensor utilized a pH-sensitive metal-oxide material for the concurrent isothermal amplification and label-free detection of nucleic acids. Based on a pH-sensitive hydrated iridium oxide oxyhydroxide film (HIROF), the electrode transforms the hydrogen ion compound generated during nucleic acid amplification into potential, so as to achieve a real-time detection. The results can be transmitted to a smartphone via Bluetooth. Moreover, HIROF was applied in nucleic acid device detection, with a super-Nernst sensitivity of 77.6 mV/pH in the pH range of 6.0-8.5, and the sensitivity showed the best results so far. Detection of V. parahaemolyticus by this novel method showed a detection limit of 1.0 × 103 CFU/mL, while the time consumption was only 30 min, outperforming real-time fluorescence loop-mediated isothermal amplification (LAMP). Therefore, the characteristics of compact, portable, and fast make the sensor more widely used in on-site detection.
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Técnicas Eletroquímicas , Irídio , Vibrio parahaemolyticus , Vibrio parahaemolyticus/isolamento & purificação , Vibrio parahaemolyticus/genética , Concentração de Íons de Hidrogênio , Técnicas Eletroquímicas/métodos , Irídio/química , Técnicas de Amplificação de Ácido Nucleico/métodos , Técnicas Biossensoriais/métodos , Limite de Detecção , EletrodosRESUMO
PURPOSE: To explore the critical role of the tumor margin irregularity degree (TMID) of renal tumors in predicting adverse pathology of patients with clinical T1/2 (cT1/2) renal cell carcinoma (RCC). METHODS: A total of 821 patients with cT1/2 RCC undergoing nephrectomy in the Second Hospital of Tianjin Medical University between January 2017 and December 2020 were reviewed. The tumor margin irregularity (TMI) was classified into renal mass with locally raised protrusion and smooth margin called 'lobular', sharply and unsmooth nodular margin called 'spiculation', blurred margins between tumor and renal parenchyma or a completely irregular and non-elliptical shape. The ratio between the number of irregular cross-sections (X) and the number of total cross-sections from top to bottom occupied (Y) was defined as TMID (X/Y). The logistic regression was performed to determine the independent predictors of adverse pathology, and the Kaplan-Meier curve and log-rank test were used to analyze the survival outcomes. RESULTS: Among 821 cT1/2 RCC patients, 245 (29.8%) had adverse pathology. The results of the univariate and multivariate logistic regressions showed that the age, tumor size, hemoglobin, and TMID were the independent predictors of adverse pathology. Incorporation of TMID could increase the discrimination of the predictive model with the area under curve (AUC) of ROC curves increasing from 0.725 to 0.808. Patients with adverse pathology or higher TMID both had significantly shorter recurrence-free survival (RFS). CONCLUSION: The nomogram model incorporated with TMID for predicting adverse pathology could increase its discrimination, calibration, and clinical application values, compared with the models without TMID.
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Carcinoma de Células Renais , Neoplasias Renais , Humanos , Carcinoma de Células Renais/cirurgia , Neoplasias Renais/cirurgia , Rim , Área Sob a Curva , HospitaisRESUMO
Intercropping with hyperaccumulators can facilitate the safe utilization of cadmium-contaminated soil. However, the effectiveness of this approach is influenced by plant species and varieties, which necessitates research on optimal plant consortia. In this study, 8 tomato varieties (3 cherry tomatoes and 5 common large-fruit tomatoes) were intercropped with Sedum alfredii in a moderately Cd-contaminated vegetable field. The results showed that the Cd concentration in the fruits of common large-fruit tomato varieties under monoculture was 1.03-1.50â¯mg/kg, while that in the fruits of cherry tomato varieties was 0.67-0.71â¯mg/kg. After intercropping with S. alfredii, the fruit Cd concentrations of Hangza 501, Hangza 503, and Hangza 108 decreased by 16.42â¯%, 19.72â¯%, and 6.76â¯%, respectively, while those of the other varieties significantly increased, except for those of Hangza 8. In contrast, the shoot Cd concentration of cherry tomatoes was greater than that of large-fruit tomatoes under monoculture. Furthermore, a significant increase in the shoot Cd concentration was noted in the Hangza 501, Hangza 503 and Hangza 603 plants following intercropping. Additionally, intercropping with S. alfredii increased the concentration of soluble sugars in the fruits of Hangza 8, Hangza 501, Hangza 503 and Hangza 603 by 4.66â¯%, 17.91â¯%, 10.60â¯% and 17.88â¯%, respectively. Intercropping with tomatoes resulted in a decrease in both the biomass and Cd uptake of S. alfredii. Interestingly, the inhibitory effect on S. alfredii was less pronounced when intercropped with cherry tomatoes than when intercropped with large-fruit tomatoes. Among the intercropping treatments, S. alfredii exhibited the greatest total Cd accumulation (0.06â¯mg/plant) when intercropped with Hangza 503. In conclusion, the cherry tomato variety Hangza 503 was the most suitable for intercropping with S. alfredii and can be used safely for vegetable production and simultaneous phytoremediation of polluted soil. Our findings suggest that strategic selection of tomato varieties can optimize the effectiveness of "phytoextraction coupled with agro-safe production" technology for managing soil Cd concentrations.
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Biodegradação Ambiental , Cádmio , Frutas , Poluentes do Solo , Solanum lycopersicum , Solanum lycopersicum/metabolismo , Solanum lycopersicum/crescimento & desenvolvimento , Cádmio/metabolismo , Cádmio/análise , Poluentes do Solo/análise , Poluentes do Solo/metabolismo , Frutas/metabolismo , Sedum/metabolismo , Solo/química , Brotos de Planta/metabolismo , Brotos de Planta/crescimento & desenvolvimento , Agricultura/métodosRESUMO
Application of microbial agents is a novel strategy to improve the quality and health of plant, which can be used to increase zinc (Zn) uptake and alleviate Zn toxicity. Here, endophytic bacteria with Zn solubilizing and growth-promoting properties were isolated from hyperaccumulating ecotype (HE) of Sedum alfredii Hance and their effects on Zn absorption and accumulation of non-hyperaccumulating ecotype (NHE) were studied. The results showed that most endophytic bacteria of HE have good Zn solubilizing or growth-promoting properties. Under the condition of 20 µM ZnSO4, the biomass of NHE inoculated with SaPS1, SaEN2, SaPR2, SaBA2, SaBA3 was 2.8-3.2 times higher than that of non-inoculation control, and the Zn concentration of shoots was increased by 45.9, 89.0, 53.7, 77.5, and 42.6% after inoculation with SaPA1, SaP1, SaEN2, SaBA1, and SaBA2. Under the condition of 100 µM ZnSO4, inoculation with SaVA1, SaPS3, SaB1, SaPR1, and SaEN3 alleviated Zn stress and significantly reduced Zn concentration of shoots. Therefore, endophytic bacteria can be an effective means of improving plant Zn nutrition quality in the normal condition and benefit plant health in the stress environment.
In this study, endophytes with Zn solubilizing properties were systematically isolated from Zn hyperaccumulator Sedum alfredii Hance. The aim is to identify endophyte resources with good promoting effect on plant growth and Zn uptake, and to provide scientific basis for the development of efficient biofortified agent.
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To overcome the significant challenges associated with nitrite supply and nitrate residues in mainstream anaerobic ammonium oxidation (anammox)-based processes, this study developed a combined solid-phase denitrification (SPD) and anammox process for low-strength nitrogen removal without the addition of nitrite. The SPD step was performed in a packed-bed reactor containing poly-3-hydroxybutyrate-co-3-hyroxyvelate (PHBV) prior to employing the anammox granular sludge reactor in the continuous-flow mode. The removal efficiency of total inorganic nitrogen reached 95.7 ± 1.2% under a nitrogen loading rate of 0.18 ± 0.01 kg N·m3·d-1, and it required 1.02 mol of nitrate to remove 1 mol of ammonium nitrogen. The PHBV particles not only served as biofilm carriers for the symbiosis of hydrolytic bacteria (HB) and denitrifying bacteria (DB), but also carbon sources that facilitated the coupling of partial denitrification and anammox in the granules. Metagenomic sequencing analysis indicated that Burkholderiales was the most abundant HB genus in SPD. The metabolic correlations between DB (Betaproteobacteria, Rhodocyclaceae, and Anaerolineae) and anammox bacteria (Candidatus Brocadiac and Kuenenia) in the granules were confirmed through microbial co-occurrence networks analysis and functional gene annotations. Additionally, the genes encoding nitrate reductase (Nap) and nitrite reductase (Nir) in DB primarily facilitated nitrate reduction, thereby supplying nitric oxide to anammox bacteria for subsequent nitrogen removal with hydrazine synthase (Hzs) and hydrazine dehydrogenase (Hdh). The findings provide insights into microbial metabolism within combined SPD and anammox processes, thus advancing the development of mainstream anammox-based processes in engineering applications.
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Desnitrificação , Nitrogênio , Águas Residuárias , Nitrogênio/metabolismo , Oxirredução , Compostos de Amônio/metabolismo , Reatores Biológicos , Eliminação de Resíduos Líquidos/métodos , Esgotos/microbiologia , Bactérias/metabolismo , Bactérias/genéticaRESUMO
This study aims to explore the mechanism of Liujunzi Decoction in the treatment of 4-nitroquinoline-N-oxide(4NQO)-induced esophageal cancer in mice. One hundred mice of 35-45 days were randomized into blank, model, and low-, medium-, and high-concentration(18.2, 36.4, and 54.6 g·kg~(-1), respectively) Liujunzi Decoction groups. The mice in other groups except the blank group had free access to the water containing 100 µg·mL~(-1) 4NQO for 16 weeks for the modeling of esophageal cancer. The mice in the Liujunzi Decoction groups were fed with the diets supplemented with corresponding concentrations of Liujunzi Decoction. The body weight and organ weights were weighed for the calculation of organ indexes. The pathological changes of the esophageal tissue were observed by hematoxylin-eosin(HE) staining. Ultra performance liquid chromatography-mass spectrometry(UPLC-MS/MS) was employed to collect metabolites from mouse serum samples, screen out potential biomarkers, and predict related metabolic pathways. Compared with the blank group, the model group showed decreased spleen and stomach indexes and increased lung, esophagus, and kidney indexes. Compared with the model group, Liujunzi Decoction groups had no significant changes in the organ indexes. The HE staining results showed that Liujunzi Decoction inhibited the invasive growth and cancerization of the esophageal cancer cells. A total of 9 potential biomarkers of Liujunzi Decoction in treating esophageal cancer were screened out in this study, which were urocanic acid, 1-oleoylglycerophosphoserine, 11-deoxy prostaglandin E1, Leu-Glu-Lys-Glu,(±) 4-hydroxy-5E,7Z,10Z,13Z,16Z,19Z-docosahexaenoic acid, ureidosuccinic acid,(2R)-2,4-dihydroxy-3,3-dimethylbutanoic acid, kynurenic acid, and bicyclo prostaglandin E2, which were mainly involved in histidine, pyrimidine, alanine, aspartate, glutamate, pantothenate and tryptophan metabolism and coenzyme A biosynthesis. In summary, Liujunzi Decoction may exert the therapeutic effect on the 4NQO-induced esophageal cancer in mice by regu-lating the amino acid metabolism, inflammation, and immune function.
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Medicamentos de Ervas Chinesas , Neoplasias Esofágicas , Espectrometria de Massas em Tandem , Camundongos , Animais , Cromatografia Líquida , Metabolômica , Biomarcadores , Neoplasias Esofágicas/induzido quimicamente , Neoplasias Esofágicas/tratamento farmacológicoRESUMO
Metabolite isomers play diverse and crucial roles in various metabolic processes. However, in untargeted metabolomics analysis, it remains a great challenge to distinguish between the constitutional isomers and enantiomers of amine-containing metabolites due to their similar chemical structures and physicochemical properties. In this work, the triplex stable isotope N-phosphoryl amino acids labeling (SIPAL) is developed to identify and relatively quantify the amine-containing metabolites and their isomers by using chiral phosphorus reagents coupled with high-resolution tandem mass spectroscopy. The constitutional isomers could be effectively distinguished with stereo isomers by using the diagnosis ions in MS/MS spectra. The in-house software MS-Isomerism has been parallelly developed for high-throughput screening and quantification. The proposed strategy enables the unbiased detection and relative quantification of isomers of amine-containing metabolites. Based on the characteristic triplet peaks with SIPAL tags, a total of 854 feature peaks with 154 isomer groups are successfully recognized as amine-containing metabolites in liver cells, in which 37 amine-containing metabolites, including amino acids, polyamines, and small peptides, are found to be significantly different between liver cancer cells and normal cells. Notably, it is the first time to identify S-acetyl-glutathione as an endogenous metabolite in liver cells. The SIPAL strategy could provide spectacular insight into the chemical structures and biological functions of the fascinating amine-containing metabolite isomers. The feasibility of SIPAL in isomeric metabolomics analysis may reach a deeper understanding of the mirror-chemistry in life and further advance the discovery of novel biomarkers for disease diagnosis.
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Aminoácidos , Espectrometria de Massas em Tandem , Espectrometria de Massas em Tandem/métodos , Indicadores e Reagentes , Isomerismo , Cromatografia Líquida/métodos , Aminoácidos/química , Metabolômica/métodos , PoliaminasRESUMO
OBJECTIVES: To determine whether 3D-CT multi-level anatomical features can provide a more accurate prediction of surgical decision-making for partial or radical nephrectomy in renal cell carcinoma. METHODS: This is a retrospective study based on multi-center cohorts. A total of 473 participants with pathologically proved renal cell carcinoma were split into the internal training and the external testing set. The training set contains 412 cases from five open-source cohorts and two local hospitals. The external testing set includes 61 participants from another local hospital. The proposed automatic analytic framework contains the following modules: a 3D kidney and tumor segmentation model constructed by 3D-UNet, a multi-level feature extractor based on the region of interest, and a partial or radical nephrectomy prediction classifier by XGBoost. The fivefold cross-validation strategy was used to get a robust model. A quantitative model interpretation method called the Shapley Additive Explanations was conducted to explore the contribution of each feature. RESULTS: In the prediction of partial versus radical nephrectomy, the combination of multi-level features achieved better performance than any single-level feature. For the internal validation, the AUROC was 0.93 ± 0.1, 0.94 ± 0.1, 0.93 ± 0.1, 0.93 ± 0.1, and 0.93 ± 0.1, respectively, as determined by the fivefold cross-validation. The AUROC from the optimal model was 0.82 ± 0.1 in the external testing set. The tumor shape Maximum 3D Diameter plays the most vital role in the model decision. CONCLUSIONS: The automated surgical decision framework for partial or radical nephrectomy based on 3D-CT multi-level anatomical features exhibits robust performance in renal cell carcinoma. The framework points the way towards guiding surgery through medical images and machine learning. CLINICAL RELEVANCE STATEMENT: We proposed an automated analytic framework that can assist surgeons in partial or radical nephrectomy decision-making. The framework points the way towards guiding surgery through medical images and machine learning. KEY POINTS: ⢠The 3D-CT multi-level anatomical features provide a more accurate prediction of surgical decision-making for partial or radical nephrectomy in renal cell carcinoma. ⢠The data from multicenter study and a strict fivefold cross-validation strategy, both internal validation set and external testing set, can be easily transferred to different tasks of new datasets. ⢠The quantitative decomposition of the prediction model was conducted to explore the contribution of each extracted feature.
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Carcinoma de Células Renais , Neoplasias Renais , Humanos , Carcinoma de Células Renais/diagnóstico por imagem , Carcinoma de Células Renais/cirurgia , Carcinoma de Células Renais/patologia , Neoplasias Renais/diagnóstico por imagem , Neoplasias Renais/cirurgia , Neoplasias Renais/patologia , Estudos Retrospectivos , Nefrectomia/métodos , Tomografia Computadorizada por Raios X/métodosRESUMO
Exploring highly active peroxidase mimics at physiological pH is important for the construction of efficient and convenient colorimetric sensing platforms for detecting small biomolecules. In this work, prepared zinc pyrovanadate (Zn3V2O7(OH)2·2H2O) nanorods exhibit excellent peroxidase-like activity, which is verified by the fast oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) into a blue product (oxTMB) by H2O2 at physiological pH (pH = 7) in 2 min. In addition, the catalytic behaviors of Zn3V2O7(OH)2·2H2O as a peroxidase-like nanozyme conform to the Michaelis-Menten equation. Scavenger experiments prove that the catalytic activity of Zn3V2O7(OH)2·2H2O is ascribed to ËO2- radicals generated in the process of catalysis. Based on the peroxidase-like activity of the Zn3V2O7(OH)2·2H2O nanozyme, a fast and convenient colorimetric sensor has been constructed to detect H2O2 and epinephrine (EP) under physiological pH. The detection limit of EP is as low as 0.26 µM. In addition, the feasibility of the proposed sensor has been validated to detect H2O2 in milk and EP in serum.
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Colorimetria , Nanotubos , Peróxido de Hidrogênio/química , Zinco , Peroxidase/química , Peroxidases/química , Corantes/química , Epinefrina , Concentração de Íons de HidrogênioRESUMO
Improving the catalytic activity of artificial nanozymes to realize the real-time detection of small molecules becomes an important task. Herein, a highly active nanozyme, 2(3), 9(10), 16(17), 23(24)-octamethoxyphthalocyanine (Pc(OH)8) modified CoFe LDH microspheres (Pc(OH)8-CoFe LDH) have been prepared by the two-step hydrothermal method. The 3,3',5,5'-tetramylbenzidine (TMB), a chromogenic substrate, was fast oxidized into blue oxTMB by H2O2 in the presence of Pc(OH)8-CoFe LDH, indicating that Pc(OH)8-CoFe LDH possesses high peroxidase-like activity rather than pure CoFe LDH. The enhancement peroxidase-like activity of the Pc(OH)8-CoFe LDH is ascribed to the synergistic action between Pc(OH)8 and CoFe LDH. Experimental results of radical scavenger and fluorescence probe verify that superoxide radical (â¢O2-) plays an important role during the catalytic reaction. Interestingly, the absorption intensity of reaction system has been enhanced largely, due to adding of the reducing substances containing catechol structure. Based on this, the three reducing substances (dopamine, procyanidin B2, catechins) containing catechol structure were distinguished from other reducing substances without catechol structure. Thus, a colorimetric array has been constructed using reaction time as the sensing element to realize the sensitive and selective recognition of catechol structures at a certain concentration.
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Peróxido de Hidrogênio , Peroxidase , Peróxido de Hidrogênio/química , Peroxidase/química , Peroxidases , Corantes Fluorescentes , Catecóis , Colorimetria/métodosRESUMO
BACKGROUND: Current research related to electroencephalogram (EEG)-based driver's emergency braking intention detection focuses on recognizing emergency braking from normal driving, with little attention to differentiating emergency braking from normal braking. Moreover, the classification algorithms used are mainly traditional machine learning methods, and the inputs to the algorithms are manually extracted features. METHODS: To this end, a novel EEG-based driver's emergency braking intention detection strategy is proposed in this paper. The experiment was conducted on a simulated driving platform with three different scenarios: normal driving, normal braking and emergency braking. We compared and analyzed the EEG feature maps of the two braking modes, and explored the use of traditional methods, Riemannian geometry-based methods, and deep learning-based methods to predict the emergency braking intention, all using the raw EEG signals rather than manually extracted features as input. RESULTS: We recruited 10 subjects for the experiment and used the area under the receiver operating characteristic curve (AUC) and F1 score as evaluation metrics. The results showed that both the Riemannian geometry-based method and the deep learning-based method outperform the traditional method. At 200 ms before the start of real braking, the AUC and F1 score of the deep learning-based EEGNet algorithm were 0.94 and 0.65 for emergency braking vs. normal driving, and 0.91 and 0.85 for emergency braking vs. normal braking, respectively. The EEG feature maps also showed a significant difference between emergency braking and normal braking. Overall, based on EEG signals, it was feasible to detect emergency braking from normal driving and normal braking. CONCLUSIONS: The study provides a user-centered framework for human-vehicle co-driving. If the driver's intention to brake in an emergency can be accurately identified, the vehicle's automatic braking system can be activated hundreds of milliseconds earlier than the driver's real braking action, potentially avoiding some serious collisions.
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Eletroencefalografia , Intenção , Humanos , Algoritmos , Aprendizado de Máquina , Curva ROCRESUMO
Granular sludges are commonly microbial aggregates used to apply partial nitritation/anammox (PN/A) processes during efficient biological nitrogen removal from ammonium-rich wastewater. Considering keystone taxa of anammox bacteria (AnAOB) in granules and their sensitivity to unfavorable environments, it is essential to investigate microbial responses of autotrophic PN/A granules to real water matrices containing organic and inorganic pollutants. In this study, tap water, surface water, and biotreated wastewater effluents were fed into a series of continuous PN/A granular reactors, respectively, and the differentiation in functional activity, sludge morphology, microbial community structure, and nitrogen metabolic pathways was analyzed by integrating kinetic batch testing, size characterization, and metagenomic sequencing. The results showed that feeding of biotreated wastewater effluents causes significant decreases in nitrogen removal activity and washout of AnAOB (dominated by Candidatus Kuenenia) from autotrophic PN/A granules due to the accumulation of heavy metals and formation of cavities. Microbial co-occurrence networks and nitrogen cycle-related genes provided evidence for the high dependence of symbiotic heterotrophs (such as Proteobacteria, Chloroflexi, and Bacteroidetes) on anammox metabolism. The enhancement of Nitrosomonas nitritation in the granules would be considered as an important contributor to greenhouse gas (N2O) emissions from real water matrices. In a novel view on the application of microbial responses, we suggest a bioassay of PN/A granules by size characterization of red-color cores in ecological risk assessment of water environments.
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Compostos de Amônio , Esgotos , Esgotos/microbiologia , Águas Residuárias , Água , Oxidação Anaeróbia da Amônia , Reatores Biológicos/microbiologia , Compostos de Amônio/química , Compostos de Amônio/metabolismo , Bactérias/genética , Bactérias/metabolismo , Oxirredução , Nitrogênio/metabolismoRESUMO
BACKGROUND: The lower limb mechanical axis was used to assess the severity of knee osteoarthritis (KOA) with varus/valgus deformity and the accuracy of targeted lower limb alignment correction after operation by conventional X-rays. There are lots of parameters to assess the gait in elder patients such as velocity, stride length, step width and swing/stance ratio by knee joint movement analysis system. However, the correlation between the lower limb mechanical axis and gait parameters is not clear. This study is aimed at obtaining the accuracy of the lower limb mechanical axis by the knee joint movement analysis system and the correlation between the lower limb mechanical axis and gait parameters. METHODS: We analysed 3D knee kinematics during ground gait of 99 patients with KOA and 80 patients 6 months after the operations with the vivo infrared navigation 3D portable knee joint movement analysis system (Opti-Knee®, Innomotion Inc, Shanghai, China). The HKA (Hip-Knee-Ankle) value was calculated and compared to X-ray findings. RESULTS: HKA absolute variation after the operation was 0.83 ± 3.76°, which is lower than that before the operation (5.41 ± 6.20°, p = 0.001) and also lower than the entire cohort (3.36 ± 5.72). Throughout the cohort, a significant correlation with low coefficients (r = -0.19, p = 0.01) between HKA value and anterior-posterior displacement was found. In comparing the HKA values measured on the full-length alignment radiographs and 3D knee joint movement analysis system (Opti-Knee), there was a significant correlation with moderate to high coefficients (r = 0.784 to 0.976). The linear correlation analysis showed that there was a significant correlation between the values of HKA measured by X-ray and movement analysis system (R2 = 0.90, p < 0.01). CONCLUSIONS: Data with equivalent results as HKA, the 6DOF of the knee and ground gait data could be provided by infrared navigation based 3D portable knee joint movement analysis system comparing with the conventional X-rays. There is no significant effect of HKA on the kinematics of the partial knee joint.
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Tornozelo , Osteoartrite do Joelho , Humanos , Idoso , Raios X , China , Articulação do Joelho/diagnóstico por imagem , Articulação do Joelho/cirurgia , Extremidade Inferior , Osteoartrite do Joelho/diagnóstico por imagem , Osteoartrite do Joelho/cirurgia , Marcha , Postura , Estudos RetrospectivosRESUMO
Extreme multistability (EM) is characterized by the emergence of infinitely many coexisting attractors or continuous families of stable states in dynamical systems. EM implies complex and hardly predictable asymptotic dynamical behavior. We analyze a model for pendulum clocks coupled by springs and suspended on an oscillating base and show how EM can be induced in this system by specifically designed coupling. First, we uncover that symmetric coupling can increase the dynamical complexity. In particular, the coexistence of multiple isolated attractors and continuous families of stable periodic states is generated in a symmetric cross-coupling scheme of four pendulums. These coexisting infinitely many states are characterized by different levels of phase synchronization between the pendulums, including anti-phase and in-phase states. Some of the states are characterized by splitting of the pendulums into groups with silent sub-threshold and oscillating behavior, respectively. The analysis of the basins of attraction further reveals the complex dependence of EM on initial conditions.
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The peroxidase-like activity of CdV2O6 nanorods has been considerably improved by modification with N, N-dicarboxymethyl perylene-diimide (PDI) as a photosensitizer. The peroxidase-like behaviors are evaluated by virtue of the colorless chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB), which is fast changed into blue oxTMB in the presence of H2O2 in only 90 s. PDI-CdV2O6 exhibits high stability at elevated temperatures and PDI-CdV2O6 retains more than 70% of its catalytic activity over a wide range of 15 to 60 °C. The catalytic mechanism of PDI-CdV2O6 is ascribed to the synergistic interaction between PDI and CdV2O6 and the generation of â¢O2- radicals. Based on the enhanced peroxidase-like activity of PDI-CdV2O6, a selective colorimetric sensor has been constructed for H2O2 and pyrogallol (PG) with detection limits of 36.5 µM and 0.179 µM, respectively. The feasibility of the proposed sensing platform has been validated by detecting H2O2 in milk and pyrogallol in tap water.
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PqqB from Methylobacterium extorquens is a unique nonheme iron-dependent hydroxylase involved in the biosynthesis of redox cofactor pyrroloquinoline quinone (PQQ). A series of recent experiments have demonstrated that PqqB catalyzes the stepwise insertions of two oxygen atoms into the tyrosine ring of the diamino acid substrate, generating the quinone moiety of PQQ; however, the reaction details have not been elucidated yet. In this paper, on the basis of the crystal structures, the enzyme-substrate complex models were constructed, and the catalytic mechanism of PqqB was explored by performing a series of combined QM/MM calculations. Our results confirmed that the first hydroxylation is performed by the highly reactive FeIV-oxo species and follows the typical H-abstraction/hydroxyl rebound mechanism, which is similar to the common aliphatic hydroxylation catalyzed by the α-KG enzymes. Nevertheless, the second hydroxylation is achieved by the Fe-O2 species, and the reactant complex can be described as an intermediate radical-FeII-superoxide, that is, the dioxygen is activated by accepting an electron from the bidentate coordination intermediate. Since both the dioxygen and intermediate are activated by electron transfer, the distal oxygen of superoxide can directly attack the carbonyl carbon of substrate to form an alkylperoxo intermediate, then the O-O heterolysis occurs to afford the epoxide intermediate, which finally evolves into the product by rearrangement. It is the bidentate coordination of catechol moiety to iron that leads to the one-electron oxidation of the substrate by the dioxygen, which significantly activates the substrate and promotes the superoxide radical attack. During the catalysis, Asp90 and His240 in the second sphere play an important role by acting as acid-base catalysts to mediate the proton transfer and manipulate the suitable orientation of superoxide. These findings may provide useful information for understanding the unique reaction mechanism of PqqB that employs both the FeIV-oxo and FeII-superoxide to carry out the aromatic hydroxylation.
Assuntos
Oxigenases de Função Mista , Cofator PQQ , Catálise , Compostos Ferrosos , Hidroxilação , Ferro , Oxirredução , Oxigênio , Cofator PQQ/metabolismo , SuperóxidosRESUMO
Hafnium (Hf)-based UiO-66 series metal-organic frameworks (MOFs) have been widely studied on gas storage, gas separation, reduction reaction, and other aspects since they were first prepared in 2012, but there are few studies on proton conductivity. In this work, one Hf-based MOF, Hf-UiO-66-fum showing UiO-66 structure, also known as MOF-801-Hf, was synthesized at room temperature using cheap fumaric acid as the bridging ligand, and then imidazole units were successfully introduced into MOF-801-Hf to obatin a doped product, Im@MOF-801-Hf. Note that both MOF-801-Hf and Im@MOF-801-Hf demonstrate excellent thermal, water, and acid-base stabilities. Expectedly, the maximum proton conductivity (σ) of Im@MOF-801-Hf (1.46 × 10-2 S·cm-1) is nearly 4 times greater than that of MOF-801-Hf (3.98 × 10-3 S·cm-1) under 100 °C and 98% relative humidity (RH). To explore their possible practical application value, we doped them into chitosan (CS) or Nafion membranes as fillers, namely, CS/MOF-801-Hf-X, CS/Im@MOF-801-Hf-Y, and Nafion/MOF-801-Hf-Z (X, Y, and Z are the doping percentages of MOF in the membrane, respectively). Intriguingly, it was found that CS/MOF-801-Hf-6 and CS/Im@MOF-801-Hf-4 indicated the highest σ values of 1.73 × 10-2 and 2.14 × 10-2 S·cm-1, respectively, under 100 °C and 98% RH and Nafion/MOF-801-Hf-9 also revealed a high σ value of 4.87 × 10-2 S·cm-1 under 80 °C and 98% RH, which showed varying degrees of enhancement compared to the original MOFs or pure CS and Nafion membranes. Our study illustrates that these Hf-based MOFs and related composite membranes offer great potential in electrochemical fields.
Assuntos
Quitosana , Estruturas Metalorgânicas , Polímeros de Fluorcarboneto , Háfnio , Estruturas Metalorgânicas/química , Ácidos Ftálicos , PrótonsRESUMO
Finding more metal complexes with outstanding water stability and high proton conductivity still has important research significance for the energy field. Herein, two highly proton-conductive complexes, one hydrogen-bonded supramolecular framework (HSF) [Cd(CBIA)2(H2O)4]·2H2O (1) and one coordination polymer (CP), {[Cd2(CBIA)2(4,4'-bipy)2(H2O)2]·(CBIA)·(OH)·2H2O}n (2) (4,4'-bipy = 4,4'-bipyridine), were triumphantly assembled using a zwitterionic organic compound, 2-(1-(carboxymethyl)-1H-benzo[d]imidazol-3-ium-3-yl)acetate (HCBIA). In the structure of HSF 1, there are several coordination and lattice H2O units except for the two monodentate CBIA- anions. CP 2 with a one-dimensional (1D) cylindrical structure has free CBIA- units and free H2O units located in the cavity. Thanks to the ability of the uncoordinated carboxyl groups and coordination/lattice water molecules to construct the rich H-bonding networks, both complexes exhibit super-high proton conductivities, reaching 5.09 × 10-3 and 3.41 × 10-3 S cm-1 under 100 °C/98% relative humidity (RH), respectively. Based on the exploration of crystal structure data, combined with the calculated activation energy, and adsorption/desorption plots of nitrogen and water vapor, the causes and differences in proton conductivity of the two complexes, especially the proton-conductive mechanism, are compared and analyzed. This study again confirms that the zwitterionic ligands can exert important effects on forming organo-inorganic hybrid materials with high proton conductivity.