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Quantitative understanding of the chemisorption on single-atom catalysts (SACs) by their electronic properties is crucial for the catalyst design. However, the physical mechanism is still under debate. Here, the CO catalytic oxidation on single transition metal (i.e., Sc, Ti, V, Cr, Mn, Fe, Co, Ni) dopants is used as a theoretical model to explore the correlations between the characteristics of electronic structures and the chemisorption on SACs. For these metal dopants, their atomic d orbitals form several nondegenerate and localized electronic states that are found to be selectively coupled with the π* orbital of the adsorbed O2, which we defined as selective orbital coupling. Based on the selective orbital coupling, we find that the alignment between the selected d state and the π* state determines the bond strength, regardless of the electron occupation number of the selected d states; the electron transfer to form M-O bonding can be provided by the support. Such electron transfer can be related with the electronic metal-support interaction. We attribute the origin of the chemisorption mechanism to the coexistence of the localized orbital of the single transition metal and the continuous energy band of the Au support. Finally, we illustrate how this mechanism dominates the variation trend of the reaction barriers. Our results unravel a fundamental adsorption mechanism in SAC systems.
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BACKGROUND: Pediatric-type diffuse high-grade glioma (pHGG) is the most frequent malignant brain tumor in children and can be subclassified into multiple entities. Fusion genes activating the MET receptor tyrosine kinase often occur in infant-type hemispheric glioma (IHG) but also in other pHGG and are associated with devastating morbidity and mortality. METHODS: To identify new treatment options, we established and characterized two novel orthotopic mouse models harboring distinct MET fusions. These included an immunocompetent, murine allograft model and patient-derived orthotopic xenografts (PDOX) from a MET-fusion IHG patient who failed conventional therapy and targeted therapy with cabozantinib. With these models, we analyzed the efficacy and pharmacokinetic properties of three MET inhibitors, capmatinib, crizotinib and cabozantinib, alone or combined with radiotherapy. RESULTS: Capmatinib showed superior brain pharmacokinetic properties and greater in vitro and in vivo efficacy than cabozantinib or crizotinib in both models. The PDOX models recapitulated the poor efficacy of cabozantinib experienced by the patient. In contrast, capmatinib extended survival and induced long-term progression-free survival when combined with radiotherapy in two complementary mouse models. Capmatinib treatment increased radiation-induced DNA double-strand breaks and delayed their repair. CONCLUSIONS: We comprehensively investigated the combination of MET inhibition and radiotherapy as a novel treatment option for MET-driven pHGG. Our seminal preclinical data package includes pharmacokinetic characterization, recapitulation of clinical outcomes, coinciding results from multiple complementing in vivo studies, and insights into molecular mechanism underlying increased efficacy. Taken together, we demonstrate the groundbreaking efficacy of capmatinib and radiation as a highly promising concept for future clinical trials.
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Neoplasias Encefálicas , Glioma , Proteínas Proto-Oncogénicas c-met , Ensayos Antitumor por Modelo de Xenoinjerto , Animales , Humanos , Glioma/patología , Glioma/tratamiento farmacológico , Glioma/genética , Glioma/terapia , Proteínas Proto-Oncogénicas c-met/antagonistas & inhibidores , Proteínas Proto-Oncogénicas c-met/genética , Proteínas Proto-Oncogénicas c-met/metabolismo , Ratones , Neoplasias Encefálicas/patología , Neoplasias Encefálicas/tratamiento farmacológico , Neoplasias Encefálicas/genética , Neoplasias Encefálicas/radioterapia , Benzamidas/farmacología , Benzamidas/uso terapéutico , Línea Celular Tumoral , Proteínas de Fusión Oncogénica/genética , Proteínas de Fusión Oncogénica/metabolismo , Femenino , Inhibidores de Proteínas Quinasas/farmacología , Inhibidores de Proteínas Quinasas/uso terapéutico , Piridinas/farmacología , Piridinas/uso terapéutico , Crizotinib/farmacología , Crizotinib/uso terapéutico , Modelos Animales de Enfermedad , Niño , Clasificación del Tumor , Anilidas/farmacología , Imidazoles , TriazinasRESUMEN
Inaccuracies in ion detection and signal processing can undermine confidence in the molecular formula assignment of high-resolution mass spectrometry, which relies on precise matching of the mass-to-charge ratio (m/z). This study proposes a novel graph-based spectra calibration method, MSCMcalib, which implements coordinate transformation and pattern detection. MSCMcalib maps uncalibrated m/z data onto a modified 2D mass defect plot, facilitating the automatic calibration of detected lines, i.e., the calibration of uncalibrated peaks aligned with these lines. The "propagation" method is subsequently employed to accurately and automatically calibrate 605 m/z values across multiple lines, encompassing 98% of the m/z range. The calibrated m/z values divide the m/z range of the spectrum into multiple subintervals, with each subinterval undergoing a process of "scaling" calibration. The utilization of narrower partitions effectively mitigates divergence issues at both ends that arise from the polynomial fitting of errors against m/z. The effectiveness of MSCMcalib is validated through the calibration of SRFA data with m/z error ranges spanning from -10 to -6 ppm, resulting in an additional assignment of 11%-30% more molecular formulas compared to the quadratic fitting calibration.
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Hosts hold great prospects for addressing the dendrite growth and volume expansion of the Li metal anode, but Li dendrites are still observable under the conditions of high deposition capacity and/or high current density. Herein, a nitrogen-doped graphene mesh (NGM) is developed, which possesses a conductive and lithiophilic scaffold for efficient Li deposition. The abundant nanopores in NGM can not only provide sufficient room for Li deposition, but also speed up Li ion transport to achieve a high-rate capability. Moreover, the evenly distributed N dopants on the NGM can guide the uniform nucleation of Li so that to inhibit dendrite growth. As a result, the composite NGM@Li anode shows satisfactory electrochemical performances for Li-S batteries, including a high capacity of 600 mAh g-1 after 300 cycles at 1 C and a rate capacity of 438 mAh g-1 at 3 C. This work provides a new avenue for the fabrication of graphene-based hosts with large areal capacity and high-rate capability for Li metal batteries.
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The hepatitis B virus (HBV) core protein (HBc) functions in multiple steps of the viral life cycle. Heteroaryldihydropyrimidine compounds (HAPs) such as Bay41-4109 are capsid protein allosteric modulators that accelerate HBc degradation and inhibit the virion secretion of HBV, specifically by misleading HBc assembly into aberrant non-capsid polymers. However, the subsequent cellular fates of these HAP-induced aberrant non-capsid polymers are not well understood. Here, we discovered that that the chaperone-binding E3 ubiquitin ligase protein STUB1 is required for the removal of Bay41-4109-induced aberrant non-capsid polymers from HepAD38 cells. Specifically, STUB1 recruits BAG3 to transport Bay41-4109-induced aberrant non-capsid polymers to the perinuclear region of cells, thereby initiating p62-mediated macroautophagy and lysosomal degradation. We also demonstrate that elevating the STUB1 level enhances the inhibitory effect of Bay41-4109 on the production of HBeAg and HBV virions in HepAD38 cells, in HBV-infected HepG2-NTCP cells, and in HBV transgenic mice. STUB1 overexpression also facilitates the inhibition of Bay41-4109 on the cccDNA formation in de novo infection of HBV. Understanding these molecular details paves the way for applying HAPs as a potentially curative regimen (or a component of a combination treatment) for eradicating HBV from hepatocytes of chronic infection patients.
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Antivirales/farmacología , Proteínas de la Cápside/efectos de los fármacos , Virus de la Hepatitis B/efectos de los fármacos , Virus de la Hepatitis B/metabolismo , Ubiquitina-Proteína Ligasas/metabolismo , Animales , Proteínas de la Cápside/metabolismo , Hepatitis B/virología , Humanos , Macroautofagia/efectos de los fármacos , RatonesRESUMEN
PURPOSE: Cancer survivors have a high risk of mortality, and vitamin D (VD) is associated with the risk of mortality. This study is aim to examine the impact of VD on mortality in cancer survivors. METHODS: A prospective study was conducted using data from the National Health and Nutrition Examination Survey. Participants were obtained information on their baseline characteristics, dietary habits, comorbidities, lifestyle, and serum 25-hydroxy VD [25(OH)D] concentrations. The weighted Cox proportional hazard and competing risk regression models were used to estimate the hazard ratio and 95% confidence intervals (HR, 95% CI) of mortality for different serum 25(OH)D concentrations. Restricted cubic spline (RCS) curves were utilized to illustrate the dose-response relationship between serum 25(OH)D concentrations and mortality. RESULTS: The study encompassed 2,495 participants with cancer diagnoses. Multivariate models indicated that, compared to serum 25(OH)D concentrations below 58.5 nmol/L, concentrations exceeding 81.6 nmol/L were associated with reduced HRs for all-cause mortality (HR = 0.70; 95% CI: 0.56-0.87), cardiovascular mortality (HR = 0.53; 95% CI: 0.32-0.86), and cancer-specific mortality (HR = 0.66; 95% CI: 0.45-0.99). RCS curves revealed "L-shaped" associations between serum 25(OH)D concentration and both all-cause and cancer-specific mortality, with threshold effects at 87.9 nmol/L and 84.6 nmol/L, respectively. Conversely, the relationship between serum 25(OH)D concentration and cardiovascular mortality exhibited a more linear pattern, with a threshold at 88.7 nmol/L. Subgroup analyses highlighted a gender-specific interaction that elevated serum 25(OH)D concentrations were significantly more protective against mortality in males than in females, especially regarding cancer-specific mortality (P-interaction = 0.009). CONCLUSION: Elevated serum 25(OH)D concentrations were correlated with decreased risks of all-cause, cardiovascular, and cancer-specific mortality in cancer survivors, with benefit thresholds at 87.9, 88.7, and 84.6 nmol/L, respectively. These findings suggested that cancer survivors might benefit from higher vitamin D recommendations than the general population.
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Supervivientes de Cáncer , Neoplasias , Encuestas Nutricionales , Vitamina D , Vitamina D/análogos & derivados , Humanos , Vitamina D/sangre , Masculino , Femenino , Persona de Mediana Edad , Supervivientes de Cáncer/estadística & datos numéricos , Estados Unidos/epidemiología , Estudios Prospectivos , Neoplasias/mortalidad , Neoplasias/sangre , Anciano , Adulto , Factores de Riesgo , Modelos de Riesgos Proporcionales , Enfermedades Cardiovasculares/mortalidad , Enfermedades Cardiovasculares/sangreRESUMEN
Electrochemical C-H mono/multi-bromination regulation of N-sulfonylanilines on the cost-effective CF electrode is described. This reaction proceeds smoothly under mild conditions with a broad substrate scope, affording diverse mono/multi-brominated anilines in moderate to good yields. Mechanism study reveals that this transformation involves anodic oxidation, aromatic electrophilic substitution, and deprotonation. Preliminary electroactive molecule screening results in its prospective application in electroactive MBs for electrochemical biosensors.
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A photocatalytic annulation cascade of unactivated N-alkene-linked indoles with Langlois' reagent by a radical relay is developed at room temperature under blue LED irradiation. The reaction afforded a series of tri/difluoromethylated pyrrolo[1,2-a]indoles in moderate to good yields. The DFT study suggests that the reaction is ascribed to a rhodamine 6G-induced cyclization cascade involving vinyl addition-radical relay and hydrogen-atom-abstraction (HAA) processes, and interestingly, pyrrolo[1,2-a]indoles are applied as fluorescent dyes into the fluorescence spectrum and live-cell imaging. This paper represents an initial example on photocatalytic cyclization cascades by radical relay and the HAA process.
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Dissolved organic matter (DOM), the most reactive fraction of forest soil organic matter, is increasingly impacted by wildfires worldwide. However, few studies have quantified the temporal changes in soil DOM quantity and quality after fire. Here, soil samples were collected after the Qipan Mountain Fire (3-36 months) from pairs of burned and unburned sites. DOM contents and characteristics were analyzed using carbon quantification and various spectroscopic and spectrometric techniques. Compared with the unburned sites, burned sites showed higher contents of bulk DOM and most DOM components 3 months after the fire but lower contents of them 6-36 months after the fire. During the sharp drop of DOM from 3 to 6 months after the fire, carboxyl-rich alicyclic molecule-like and highly unsaturated compounds had greater losses than condensed aromatics. Notably, the burned sites had consistently higher abundances of oxygen-poor dissolved black nitrogen and fluorescent DOM 3-36 months after the fire, particularly the abundance of pyrogenic C2 (excitation/emission maxima of <250/â¼400 nm) that increased by 150% before gradually declining. This study advances the understanding of temporal variations in the effects of fire on different soil DOM components, which is crucial for future postfire environmental management.
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Incendios , Suelo , Suelo/química , China , Incendios Forestales , BosquesRESUMEN
The bioavailable diverse dissolved organic matter (DOM) present in glacial meltwater significantly contributes to downstream carbon cycling in mountainous regions. However, the comprehension of molecular-level characteristics of riverine DOM, from tributary to downstream and their fate in glacier-fed desert rivers remains limited. Herein, we employed spectroscopic and high-resolution mass spectrometry techniques to study both optical and molecular-level characteristics of DOM in the Tarim River catchment, northwest China. The results revealed that the DOC values in the downstream were higher than those in the tributaries, yet they remained comparable to those found in other glacier-fed streams worldwide. Five distinct components were identified using EEM-PARAFAC analysis in both tributary and downstream samples. The dominance of three protein-like components in tributary samples, contrasting with a higher presence of humic-like components in downstream samples, which implied that the dilution and alterations of the glacier DOM signature and overprinting with terrestrial-derived DOM. Molecular composition revealed that thousands of compounds with higher molecular weight and increased aromaticity were transformed, generated and introduced from terrestrial inputs during downstream transportation. The twofold rise in polycyclic aromatic and polyphenolic compounds observed downstream compared to tributaries indicated a greater influx of terrestrial organic matter introduced into the downstream during water transportation. The study suggests that the glacier-sourced DOM experienced minimal photodegradations, with limited influence from human activities, while also being shaped by terrestrial inputs during its transit in the alpine-arid region. This unique scenario offers valuable insights into comprehending the fate of DOM originating from glacial meltwater in arid mountainous regions.
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Cubierta de Hielo , Ríos , China , Ríos/química , Cubierta de Hielo/química , Monitoreo del Ambiente/métodos , Compuestos Orgánicos/análisis , Contaminantes Químicos del Agua/análisis , Sustancias Húmicas/análisis , Espectrometría de Masas , Clima DesérticoRESUMEN
BACKGROUND: -Recent evidence suggests that hyperuricemia may act as independent risk factors for erectile dysfunction (ED), in addition to the already established factors. The current evidence supporting this relationship remains insufficient. METHODS AND RESULTS: -A total of 3,810 participants from the NHANES pool between 2001 and 2004 were included in our study, comprising 1,093 individuals with ED and 2,717 individuals without ED. Univariable and multivariable logistic regression analyses were conducted to examine the relationship between uric acid (UA) and the prevalence of ED. In the fully adjusted model, no significant association was observed between UA and ED (OR = 1.02, 95% CI: 0.84-1.24), and no significant differences were noted among the various UA levels (p = 0.5). In our sensitivity analyses, employing a stricter definition for ED, no significant results were found in the fully adjusted model (OR = 0.85, 95% CI: 0.60-1.19). Furthermore, no significant differences were observed among the various UA levels (p = 0.083). CONCLUSIONS: -Our study did not establish a correlation between UA levels and ED. Nonetheless, further research with larger sample cohorts is required to verify these findings.
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Disfunción Eréctil , Encuestas Nutricionales , Ácido Úrico , Humanos , Masculino , Disfunción Eréctil/epidemiología , Disfunción Eréctil/sangre , Ácido Úrico/sangre , Estados Unidos/epidemiología , Persona de Mediana Edad , Adulto , Factores de Riesgo , Hiperuricemia/epidemiología , Hiperuricemia/sangre , Prevalencia , AncianoRESUMEN
Cerebral amyloid-ß (Aß) accumulation due to impaired Aß clearance is a pivotal event in the pathogenesis of Alzheimer's disease (AD). Considerable brain-derived Aß is cleared via transporting to the periphery. The liver is the largest organ responsible for the clearance of metabolites in the periphery. Whether the liver physiologically clears circulating Aß and its therapeutic potential for AD remains unclear. Here, we found that about 13.9% of Aß42 and 8.9% of Aß40 were removed from the blood when flowing through the liver, and this capacity was decreased with Aß receptor LRP-1 expression down-regulated in hepatocytes in the aged animals. Partial blockage of hepatic blood flow increased Aß levels in both blood and brain interstitial fluid. The chronic decline in hepatic Aß clearance via LRP-1 knockdown specific in hepatocytes aggravated cerebral Aß burden and cognitive deficits, while enhancing hepatic Aß clearance via LRP-1 overexpression attenuated cerebral Aß deposition and cognitive impairments in APP/PS1 mice. Our findings demonstrate that the liver physiologically clears blood Aß and regulates brain Aß levels, suggesting that a decline of hepatic Aß clearance during aging could be involved in AD development, and hepatic Aß clearance is a novel therapeutic approach for AD.
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Enfermedad de Alzheimer , Ratones , Animales , Enfermedad de Alzheimer/patología , Precursor de Proteína beta-Amiloide/metabolismo , Péptidos beta-Amiloides/metabolismo , Encéfalo/patología , Hígado/metabolismo , Hígado/patología , Ratones Transgénicos , Modelos Animales de EnfermedadRESUMEN
Identifying cold-related genes can provide insights into the cold adaptation mechanism of weeping forsythia. In this study, we compared the changes in gene expressions and physiological and biochemical indices under short-term cold stimulation with the changes in gene sequences under a long-term heterogeneous environment to investigate the cold adaptation mechanism in weeping forsythia. The data of adaptive gene sequence changes, e.g., single nucleotide polymorphisms, were obtained from previous landscape genomics studies. The physiological and biochemical indicators and transcriptome results showed that weeping forsythia initiated a series of programs, including increasing cell osmotic pressures, scavenging ROS, activating the defense mechanism that crosses with pathogen infection, and upregulating CBF/DREB1 transcription factor 1, to cope with short-term cold stress. A reanalysis of landscape genomic data suggested that weeping forsythia responded to long-term heterogeneous cold stress by the differentiation of genes related to synthesis of aromatic substances and adenosine triphosphate. Our results supported the hypothesis that the adaptation mechanisms of species to short-term environmental stimulation and long-term stress in heterogeneous environments are different. The differences in cold tolerance among populations are not necessarily obtained by changing cold-responsive gene sequences. This study provides new insights into the cold adaptation mechanisms of plants.
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Forsythia , Forsythia/genética , Transcriptoma , Plantas/genética , Regulación de la Expresión Génica de las Plantas , Adaptación Fisiológica/genéticaRESUMEN
Exaggerated startle has been recognized as a core hyperarousal symptom of multiple fear-related anxiety disorders, such as post-traumatic stress disorder (PTSD) and panic disorder. However, the mechanisms driving this symptom are poorly understood. Here we reveal a neural projection from dorsal raphe nucleus (DRN) to a startle-controlling center reticulotegmental nucleus (RtTg) that mediates enhanced startle response under fear condition. Within RtTg, we identify an inhibitory microcircuit comprising GABAergic neurons in pericentral RtTg (RtTgP) and glutamatergic neurons in central RtTg (RtTgC). Inhibition of this RtTgP-RtTgC microcircuit leads to elevated startle amplitudes. Furthermore, we demonstrate that the conditioned fear-activated DRN 5-HTergic neurons send inhibitory projections to RtTgP GABAergic neurons, which in turn upregulate neuronal activities of RtTgC glutamatergic neurons. Chemogenetic activation of the DRN-RtTgP projections mimics the increased startle response under fear emotions. Moreover, conditional deletion of 5-HT1B receptor from RtTgP GABAergic neurons largely reverses the exaggeration of startle during conditioned fear. Thus, our study establishes the disinhibitory DRN-RtTgP-RtTgC circuit as a critical mechanism underlying exaggerated startle under fear emotions, and provides 5-HT1B receptor as a potential therapeutic target for treating hyperarousal symptom in fear-associated psychiatric disorders.
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Miedo , Receptor de Serotonina 5-HT1B , Núcleo Dorsal del Rafe , Miedo/fisiología , Neuronas GABAérgicas/metabolismo , Neuronas GABAérgicas/fisiología , Mesencéfalo/metabolismo , Mesencéfalo/fisiología , Receptor de Serotonina 5-HT1B/genética , Receptor de Serotonina 5-HT1B/metabolismo , Reflejo de Sobresalto/fisiología , Animales , RatonesRESUMEN
Candidatus Methanoperedens-like archaea, which can use multiple electron acceptors (nitrate, iron, manganese, and sulfate) for anaerobic methane oxidation, could play an important role in reducing methane emissions from freshwater wetlands. Currently, very little is known about the distribution and community composition of Methanoperedens-like archaea in freshwater wetlands, particularly based on their alpha subunit of methyl-coenzyme M reductase (mcrA) genes. Here, the community composition, diversity, and abundance of Methanoperedens-like archaea were investigated in a freshwater wetland through high-throughput sequencing and quantitative PCR on their mcrA genes. A large number of Methanoperedens-like mcrA gene sequences (119,250) were recovered, and a total of 31 operational taxonomic units (OTUs) were generated based on 95% sequence similarity cut-off. The majority of Methanoperedens-like sequences can be grouped into three distinct clusters that were closely associated with the known Methanoperedens species which can couple anaerobic methane oxidation to nitrate or iron reduction. The community composition of Methanoperedens-like archaea differed significantly among different sampling sites, and their mcrA gene abundance was 1.49 × 106 ~ 4.62 × 106 copies g-1 dry soil in the examined wetland. In addition, the community composition of Methanoperedens-like archaea was significantly affected by the soil water content, and the archaeal abundance was significantly positively correlated with the water content. Our results suggest that the mcrA gene is a good biomarker for detection and quantification of Methanoperedens-like archaea, and provide new insights into the distribution and environmental regulation of these archaea in freshwater wetlands.
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Archaea , Humedales , Archaea/genética , Nitratos , Suelo , Filogenia , Oxidación-Reducción , Agua Dulce , Metano , Agua , Hierro , AnaerobiosisRESUMEN
BACKGROUND: The link between malnutrition and poor prognosis in cardiovascular disease has been established but the association between malnutrition and contrast-associated acute kidney injury (CA-AKI), a common complication of coronary procedures, remains poorly understood. In this study we investigated the predictive value of 3 nutritional indexes for CA-AKI in patients undergoing percutaneous coronary intervention (PCI).MethodsâandâResults: The study included a total of 6,049 consecutive patients undergoing PCI between May 2012 and September 2020, among whom 352 (5.8%) developed CA-AKI. We used the Controlling Nutritional Status (CONUT) score, the Geriatric Nutritional Risk Index (GNRI), and the Prognostic Nutritional Index (PNI) to assess the association between malnutrition risk and CA-AKI after PCI. Multivariate logistic regression analysis revealed that malnutrition, as identified by GNRI and PNI, was significantly associated with a higher risk of CA-AKI (moderate-severe malnutrition in GNRI: odds ratio [OR]=1.92, [95% confidence interval (CI), 1.27-2.85]; malnutrition in PNI: OR=1.87, [95% CI, 1.39-2.50]), whereas the CONUT score did not demonstrate a significant difference (P>0.05). Furthermore, GNRI (∆AUC=0.115, P<0.001) and PNI (∆AUC=0.101, P<0.001) exhibited superior predictive ability than the CONUT score for CA-AKI and significantly improved reclassification and discrimination in the fully adjusted model. CONCLUSIONS: Malnutrition, especially identified by the GNRI and PNI, was associated with a higher risk of CA-AKI after PCI. GNRI and PNI performed better than the CONUT score in predicting CA-AKI.
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Both ozone (O3) and UV/O3 treatment processes can effectively remove organic matter in the flocculated membrane filtration concentrate from landfill leachate, but the ozonation byproducts (OBPs) generated in the processes remain unknown. Using electrospray ionization-coupled Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), this study investigated the molecular characteristics of unknown OBPs and their formation mechanisms during the treatment of flocculated nanofiltration concentrate (FNFC) using the O3 and UV/O3 processes. The results showed that after being treated by the O3 and UV/O3 processes, the average value of the oxygen-to-carbon ratio (O/Cavg) in the FNFC organic matter increased substantially from 0.49 to 0.61-0.64 and 0.63-0.71, respectively, with an O3 dosage of 13.4-54.4 mg/min. The main OBPs were CHO and CHON compounds, which were mainly produced through oxygenation (+O2/+O3 and -H2+O2), oxidative deamination (-NH3+O2), decyclopropyl (-C3H4), and deisopropyl (-C3H6) reactions. The hydroxyl radical (â¢OH) can intensify these reactions, resulting in an abundance of OBPs with a high oxidation degree and low molecular weight. OBPs at five m/z values were fragmented and analyzed with tandem mass spectrometry, and abundant hydroxyl groups, carboxyl groups, and carbonyl groups were tentatively identified, presenting a potential toxicity to aquatic organisms. Due to the high molecular diversity of the OBPs in FNFC, their lower ΔGCoxo compared to natural fulvic acid, and potential toxicity, their impact on the water environment should be given more attention.
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Ozono , Contaminantes Químicos del Agua , Purificación del Agua , Ozono/análisis , Contaminantes Químicos del Agua/análisis , Oxidación-Reducción , Espectrometría de Masas en Tándem , Radical Hidroxilo , Purificación del Agua/métodosRESUMEN
The redox activity of Fe-bearing minerals is coupled with the transformation of organic matter (OM) in redox dynamic environments, but the underlying mechanism remains unclear. In this work, a Fe redox cycling experiment of nontronite (NAu-2), an Fe-rich smectite, was performed via combined abiotic and biotic methods, and the accompanying transformation of humic acid (HA) as a representative OM was investigated. Chemical reduction and subsequent abiotic reoxidation of NAu-2 produced abundant hydroxyl radicals (thereafter termed as ·OH) that effectively transformed the chemical and molecular composition of HA. More importantly, transformed HA served as a more premium electron donor/carbon source to couple with subsequent biological reduction of Fe(III) in reoxidized NAu-2 by Geobacter sulfurreducens, a model Fe-reducing bacterium. Destruction of aromatic structures and formation of carboxylates were mechanisms responsible for transforming HA into an energetically more bioavailable substrate. Relative to unaltered HA, transformed HA increased the extent of the bioreduction by 105%, and Fe(III) reduction was coupled with oxidation and even mineralization of transformed HA, resulting in bleached HA and formation of microbial products and cell debris. ·OH transformation slightly decreased the electron shuttling capacity of HA in bioreduction. Our results provide a mechanistic explanation for rapid OM mineralization driven by Fe redox cycling in redox-fluctuating environments.
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Compuestos Férricos , Sustancias Húmicas , Compuestos Férricos/química , Minerales/química , Oxidación-Reducción , BacteriasRESUMEN
Despite green tides (or macroalgal blooms) having multiple negative effects, it is thought that they have a positive effect on carbon sequestration, although this aspect is rarely studied. Here, during the world's largest green tide (caused by Ulva prolifera) in the Yellow Sea, the concentration of dissolved organic carbon (DOC) increased by 20-37% in intensive macroalgal areas, and thousands of new molecular formulas rich in CHNO and CHOS were introduced. The DOC molecular species derived from U. prolifera constituted â¼18% of the total DOC molecular species in the seawater of bloom area, indicating the profound effect that green tides have on shaping coastal DOC. In addition, 46% of the macroalgae-derived DOC was labile DOC (LDOC), which had only a short residence time due to rapid microbial utilization. The remaining 54% was recalcitrant DOC (RDOC) rich in humic-like substances, polycyclic aromatics, and highly aromatic compounds that resisted microbial degradation and therefore have the potential to play a role in long-term carbon sequestration. Notably, source analysis showed that in addition to the microbial carbon pump, macroalgae are also an important source of RDOC. The number of RDOC molecular species contributed by macroalgae even exceed (77 vs 23%) that contributed by microorganisms.
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Materia Orgánica Disuelta , Ulva , Eutrofización , Secuestro de Carbono , Agua de Mar , Sustancias Húmicas , ChinaRESUMEN
Natural dissolved organic matter (DOM) represents a ubiquitous molecular mixture, progressively characterized by spatiotemporal resolution. However, an inadequate comprehension of DOM molecular dynamics, especially the stochastic processes involved, hinders carbon cycling predictions. This study employs ecological principles to introduce a neutral theory to elucidate the fundamental processes involving molecular generation, degradation, and migration. A neutral model is thus formulated to assess the probability distribution of DOM molecules, whose frequencies and abundances follow a ß-distribution relationship. The neutral model is subsequently validated with high-resolution mass spectrometry (HRMS) data from various waterbodies, including lakes, rivers, and seas. The model fitting highlights the prevalence of molecular neutral distribution and quantifies the stochasticity within DOM molecular dynamics. Furthermore, the model identifies deviations of HRMS observations from neutral expectations in photochemical and microbial experiments, revealing nonrandom molecular transformations. The ecological null model further validates the neutral modeling results, demonstrating that photodegradation reduces molecular stochastic dynamics at the surface of an acidic pit lake, while random distribution intensifies at the river surface compared with the porewater. Taken together, the DOM molecular neutral model emphasizes the significance of stochastic processes in shaping a natural DOM pool, offering a potential theoretical framework for DOM molecular dynamics in aquatic and other ecosystems.