RESUMEN
Alcohol electrooxidation is pivotal for a sustainable energy economy. However, designing efficient electrocatalysts for this process is still a formidable challenge. Herein, palladium-selenium nanowires featuring distinct crystal phases: monoclinic Pd7Se2 and tetragonal Pd4.5Se for ethylene glycol electrooxidation reaction (EGOR) are synthesized. Notably, the supported monoclinic Pd7Se2 nanowires (m-Pd7Se2 NWs/C) exhibit superior EGOR activity, achieving a mass activity (MA) and specific activity (SA) of 10.4 A mgPd -1 (18.7 mA cm-2), which are 8.0 (6.7) and 10.4 (8.2) times versus the tetragonal Pd4.5Se and commercial Pd/C and surpass those reported in the literature. Furthermore, m-Pd7Se2 NWs/C displays robust catalytic activity for other alcohol electrooxidation. Comprehensive characterization and density functional theory (DFT) calculations reveal that the enhanced electrocatalytic performance is attributed to the increased formation of Pd0 on the high-index facets of the m-Pd7Se2 NWs, which lowers the energy barriers for the CâC bond dissociation in CHOHCHOH* and the CO* oxidation to CO2*. This study provides palladium-based alloy electrocatalysts exhibiting the highest mass activity reported to date for the electrooxidation of ethylene glycol, achieved through the crystalline phase engineering strategy.
RESUMEN
BACKGROUND: The link between low grip strength, diminished physical performance, and adverse health outcomes in older adults has been well-established. However, the impact of older adults who cannot complete these tests on disability and mortality rates remains unexplored without longitudinal study. METHODS: We collected data from the China Health and Retirement Longitudinal Study (CHARLS). Participants aged 60-101 were enrolled at baseline. We analyzed the prevalence of populations unable to complete handgrip strength (HGS), gait speed (GS), and five times chair stand test (FTCST). Completing risk models were used to estimate the risk of mortality and disability over seven years. RESULTS: A total of 3,768 participants were included in the analysis. The percentage of older adults unable to complete the GS and FTCST tests increased notably with age, from 2.68 to 8.90% and 2.60-20.42%, respectively. The proportion of older people unable to perform the HGS was relatively stable, ranging from 1.40 to 3.66%. Compared to older adults who can complete these tests, those who cannot perform FTCST face a significantly higher risk of mortality, with 49.1% higher risk [hazard ratio (HR) = 1.491, 95% CI = 1.156, 1.922; subdistribution hazard ratio (SHR) = 1.491, 95%CI = 1.135,1.958)]. Participants who were unable to complete the GS test had a higher risk of developing ADL disability, regardless of whether they were compared to the lowest-performing group (HR = 1.411, 95%CI = 1.037,1.920; SHR = 1.356, 95%CI = 1.030,1.785) or those who can complete the GS (HR = 1.727, 95%CI = 1.302,2.292; SHR = 1.541, 95%CI = 1.196,1.986). No statistically significant difference in the risk of developing ADL disability among older adults who were unable to complete the HGS test compared with either the poorest performing group (HR = 0.982, 95% CI = 0.578, 1.666; SHR = 1.025, 95% CI = 0.639, 1.642) or those who were able to complete the HGS test (HR = 1.008, 95% CI = 0.601, 1.688; SHR = 0.981, 95% CI = 0.619, 1.553). The risk of all-cause mortality was not significantly different for older adults who were unable to complete the HGS test compared to those with the worst performance (HR = 1.196, 95%CI = 0.709-2.020; SHR = 1.196, 95%CI = 0.674, 2.124) or those who were able to complete the test (HR = 1.462, 95%CI = 0.872-2.450; SHR = 1.462, 95%CI = 0.821,2.605). CONCLUSION: The risks of adverse events faced by older adults unable to complete the tests vary, indicating the necessity for future research to conduct separate analyses on this high-risk population.
Asunto(s)
Fuerza de la Mano , Jubilación , Humanos , Anciano , Estudios Longitudinales , Estudios de Cohortes , Rendimiento Físico FuncionalRESUMEN
BACKGROUND AND PURPOSE: Patients with hypervascular spinal tumors may have severe blood loss during tumor resection, which increases the risks of perioperative morbidity and mortality. However, the preoperative evaluation of tumor vascularity may be challenging; moreover, the reliability of the data obtained in conventional preoperative noninvasive imaging is debatable. In this study, we compared conventional magnetic resonance imaging (MRI) and subtraction computed tomography angiography (CTA) in terms of their performance in vascularity evaluation. The catheter digital subtraction angiography (DSA) technique was used as a reference standard. METHODS: This study included 123 consecutive patients with spinal tumor who underwent subtraction CTA, catheter DSA, and subsequent surgery between October 2015 and October 2021. Data regarding qualitative and semiquantitative subtraction CTA parameters and conventional MRI signs were collected for comparison with tumor vascularity graded through catheter DSA. The diagnostic performance of qualitative CTA, quantitative CTA, and conventional MRI in assessing spinal tumor vascularity was analyzed. RESULTS: Qualitative subtraction CTA was the best noninvasive imaging modality in terms of diagnostic performance (area under the receiver operating characteristic curve [AUROC], 0.95). Quantitative CTA was relatively inferior (AUROC, 0.87). MRI results had low reliability (AUROC, 0.51 to 0.59). Intratumoral hemorrhage and prominent foraminal venous plexus were found to be the specific signs for hypervascularity (specificity 93.2%). CONCLUSIONS: Qualitative subtraction CTA offers the highest diagnostic value in evaluating spinal tumor vascularity, compared to quantitative CTA and MRI. Although conventional MRI may not be a reliable approach, certain MRI signs may have high specificity, which may be crucial for assessing spinal tumor vascularity.
RESUMEN
BACKGROUND/PURPOSE: The global incidence of lip and oral cavity cancer continues to rise, necessitating improved early detection methods. This study leverages the capabilities of computer vision and deep learning to enhance the early detection and classification of oral mucosal lesions. METHODS: A dataset initially consisting of 6903 white-light macroscopic images collected from 2006 to 2013 was expanded to over 50,000 images to train the YOLOv7 deep learning model. Lesions were categorized into three referral grades: benign (green), potentially malignant (yellow), and malignant (red), facilitating efficient triage. RESULTS: The YOLOv7 models, particularly the YOLOv7-E6, demonstrated high precision and recall across all lesion categories. The YOLOv7-D6 model excelled at identifying malignant lesions with notable precision, recall, and F1 scores. Enhancements, including the integration of coordinate attention in the YOLOv7-D6-CA model, significantly improved the accuracy of lesion classification. CONCLUSION: The study underscores the robust comparison of various YOLOv7 model configurations in the classification to triage oral lesions. The overall results highlight the potential of deep learning models to contribute to the early detection of oral cancers, offering valuable tools for both clinical settings and remote screening applications.
RESUMEN
Owing to outstanding performances, nickel-based electrocatalysts are commonly used in electrochemical alcohol oxidation reactions (AORs), and the active phase is usually vacancy-rich nickel oxide/hydroxide (NiOx Hy ) species. However, researchers are not aware of the catalytic role of atom vacancy in AORs. Here, we study vacancy-induced catalytic mechanisms for AORs on NiOx Hy species. As to AORs on oxygen-vacancy-poor ß-Ni(OH)2 , the only redox mediator is electrooxidation-induced electrophilic lattice oxygen species, which can only catalyze the dehydrogenation process (e.g., the electrooxidation of primary alcohol to carboxylic acid) instead of the C-C bond cleavage. Hence, vicinal diol electrooxidation reaction involving the C-C bond cleavage is not feasible with oxygen-vacancy-poor ß-Ni(OH)2 . Only through oxygen vacancy-induced adsorbed oxygen-mediated mechanism, can oxygen-vacancy-rich NiOx Hy species catalyze the electrooxidation of vicinal diol to carboxylic acid and formic acid accompanied with the C-C bond cleavage. Crucially, we examine how vacancies and vacancy-induced catalytic mechanisms work during AORs on NiOx Hy species.
RESUMEN
To solve surface carrier recombination and sluggish water oxidation kinetics of hematite (α-Fe2 O3 ) photoanodes, herein, an attractive surface modification strategy is developed to successively deposit ultrathin CoOx overlayer and Ni single atoms on titanium (Ti)-doped α-Fe2 O3 (Ti:Fe2 O3 ) nanorods through a two-step atomic layer deposition (ALD) and photodeposition process. The collaborative decoration of ultrathin CoOx overlayer and Ni single atoms can trigger a big boost in photo-electrochemical (PEC) performance for water splitting over the obtained Ti:Fe2 O3 /CoOx /Ni photoanode, with the photocurrent density reaching 1.05 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE), more than three times that of Ti:Fe2 O3 (0.326 mA cm-2 ). Electrochemical and electronic investigations reveal that the surface passivation effect of ultrathin CoOx overlayer can reduce surface carrier recombination, while the catalysis effect of Ni single atoms can accelerate water oxidation kinetics. Moreover, theoretical calculations evidence that the synergy of ultrathin CoOx overlayer and Ni single atoms can lower the adsorption free energy of OH* intermediates and relieve the potential-determining step (PDS) for oxygen evolution reaction (OER). This work provides an exemplary modification through rational engineering of surface electrochemical and electronic properties for the improved PEC performances, which can be applied in other metal oxide semiconductors as well.
RESUMEN
OBJECTIVES: Preoperative embolization (PE) for metastatic spinal tumors is a method of minimizing intraoperative blood loss during aggressive surgery. This study specified angiographic standards and investigated the influence of these and other factors on blood loss in patients with spinal metastases and various pathologies. METHODS: The cohort comprised 126 consecutive patients receiving PE from 2015 to 2021. Their clinical, surgical, and angiographic characteristics were reviewed. Standard angiographic grading was used for vascularity assessment. Degree of embolization was divided into complete (≥ 90%), near complete (67 to < 90%), and partial (< 67%). Logistic regression analysis was used to investigate factors predictive of massive blood loss (> 2500 mL). A proportional odds model was used to assess factors predictive of the degree of embolization. RESULTS: Mean intraoperative blood loss was 1676 mL. Among the patients, 62 had hypervascular tumors and 64 had nonhypervascular tumors, according to the angiographic classification. Intraoperative blood loss differed significantly with embolization degree, both overall (p < 0.001) and in the hypervascular and nonhypervascular groups (p = 0.01 and 0.03). Angiographic hypervascularity, spinal metastasis invasiveness index, and embolization degree were significant predictors of massive blood loss in univariate analysis, but only embolization degree was significant in multivariate analysis. Only the presence of the radiculomedullary artery at the target level was significant in both the univariate and multivariate analyses for embolization degree. CONCLUSIONS: In addition to pathological classification, angiographic vascularity assessment is valuable. Although complete embolization is a reasonable goal, it is challenging to achieve in cases of visible radiculomedullary artery. KEY POINTS: ⢠Angiography has a supplementary role in vascularity assessment for spinal metastatic surgery. ⢠Better embolization degree is associated with less intraoperative blood loss in both angiographic hypervascular and nonhypervascular groups. ⢠Presence of radiculomedullary artery in the target level causes worse embolization outcome.
Asunto(s)
Embolización Terapéutica , Neoplasias de la Columna Vertebral , Humanos , Neoplasias de la Columna Vertebral/diagnóstico por imagen , Neoplasias de la Columna Vertebral/cirugía , Pérdida de Sangre Quirúrgica/prevención & control , Angiografía , Embolización Terapéutica/métodos , Procedimientos Neuroquirúrgicos , Cuidados Preoperatorios , Estudios Retrospectivos , Resultado del TratamientoRESUMEN
BACKGROUND: We aimed to investigate the interaction between serum uric acid (SUA) levels with estimated glomerular filtration rate (eGFR) to low muscle strength (LMS) among older people in China. METHODS: Cohort data were obtained from China Health and Retirement Longitudinal Study (CHARLS) in 2011 and 2015. A total of 2,822 community-dwelling adults aged 60 and above were enrolled for the follow-up. Serum uric acid was collected after 8 h of fasting, and handgrip strength was measured with a dynamometer. eGFR was calculated with an equation based on the Chinese population. A generalized additive model was employed for interaction analysis and progressively adjusted confounders. RESULTS: During the follow-up, a total of 659 individuals were excluded due to the lack of grip strength data, leaving 2,163 participants for analysis. Despite the protective effect of high uric acid against low muscle strength, especially in older females, it is not statistically significant (OR = 0.69, 95%CI = 0.45-1.04, P = 0.075). Following the progressive adjustment of covariates, the association between higher eGFR and elevated SUA levels remained statistically significant in females, showing a reduced odds ratio with low muscle strength (OR = 0.82, 95%CI = 0.70-0.97, P = 0.021). However, this trend was not observed in male participants. CONCLUSIONS: This Chinese population-based cohort study suggests that among older females, a higher serum uric acid level combined with a higher estimated glomerular filtration rate is linked to a reduced risk of low muscle strength. This implies that the relationship between high serum uric acid levels and the risk of low grip strength might differ by gender.
Asunto(s)
Fuerza de la Mano , Ácido Úrico , Femenino , Humanos , Masculino , Anciano , Tasa de Filtración Glomerular , Estudios Longitudinales , Estudios de Cohortes , Estudios Retrospectivos , Fuerza Muscular , Factores de RiesgoRESUMEN
Cephaleuros species cause algal spot diseases, also known as red rust diseases, on many plants, including fruit crops. Most algal species are defined based on their morphological characteristics. Recent phylogenetic studies of Cephaleuros species showed that morphological determination was not congruent with phylogeny. Our study examined the phylogenetic congruence of the host invasion types (or growth habits), which are the most critical characteristics in the taxonomy of Cephaleuros. To ensure that host invasion types and phylogenetic characteristics could be inferred from the same isolate, host invasion types were assessed using microanatomical observation, and rRNA sequences from the same algal spot and/or the derived algal cultures were compared. Host invasion types were found to be conserved classification traits and were congruent with Cephaleuros phylogeny. The results also indicated that more than one Cephaleuros species commonly grew on the same leaf or, in a few cases, the same algal spot, suggesting that identification using different algal spots could result in misidentification. The Cephaleuros isolates were separated into two species complexes by host invasion types: the C. virescens species complex (CVSC) with subcuticular host invasion type and the C. parasiticus species complex (CPSC) with intercellular host invasion type. Molecular phylogenetic analysis indicated that Cephaleuros isolates clustered into 14 clades of CVSC and three clades of CPSC. This study also identified 16 and eight new hosts of CVSC and CPSC in Taiwan, respectively.
Asunto(s)
Basidiomycota , Chlorophyta , Filogenia , ARN Ribosómico , FenotipoRESUMEN
Electrochemical CO2 reduction reaction (ECO2 RR) with controlled product selectivity is realized on Ag-Cu bimetallic surface alloys, with high selectivity towards C2 hydrocarbons/alcohols (≈60 % faradaic efficiency, FE), C1 hydrocarbons/alcohols (≈41 % FE) and CO (≈74 % FE) achieved by tuning surface compositions and applied potentials. In situ spectral investigations and theoretical calculations reveal that surface-composition-dependent d-band center could tune *CO binding strengths, regulating the *CO subsequent reaction pathways and then the product selectivity. Further adjusting the applied potentials will alter the energy of participated electrons, which leads to controlled ECO2 RR selectivity towards desired products. A predominant region map, with an indicator proposed to evaluate the thermodynamic predominance of the *CO subsequent reactions, is then provided as a reliable theoretical guidance for the controllable ECO2 RR product selectivity over bimetallic alloys.
RESUMEN
Due to the robust oxidation conditions in strong acid oxygen evolution reaction (OER), developing an OER electrocatalyst with high efficiency remains challenging in polymer electrolyte membrane (PEM) water electrolyzer. Recent theoretical research suggested that reducing the coordination number of Ir-O is feasible to reduce the energy barrier of the rate-determination step, potentially accelerating the OER. Inspired by this, we experimentally verified the Ir-O coordination number's role at model catalysts, then synthesized low-coordinated IrOx nanoparticles toward a durable PEM water electrolyzer. We first conducted model studies on commercial rutile-IrO2 using plasma-based defect engineering. The combined in situ X-ray absorption spectroscopy (XAS) analysis and computational studies clarify why the decreased coordination numbers increase catalytic activity. Next, under the model studies' guidelines, we explored a low-coordinated Ir-based catalyst with a lower overpotential of 231â mV@10â mA cm-2 accompanied by long durability (100â h) in an acidic OER. Finally, the assembled PEM water electrolyzer delivers a low voltage (1.72â V@1â A cm-2 ) as well as excellent stability exceeding 1200â h (@1â A cm-2 ) without obvious decay. This work provides a unique insight into the role of coordination numbers, paving the way for designing Ir-based catalysts for PEM water electrolyzers.
RESUMEN
Electronic structure modulation among multiple metal sites is key to the design of efficient catalysts. Most studies have focused on regulating 3d transition-metal active ions through other d-block metals, while few have utilized f-block metals. Herein, we report a new class of catalyst, namely, UCoO4 with alternative CoO6 and 5f-related UO6 octahedra, as a unique example of a 5f-covalent compound that exhibits enhanced electrocatalytic oxygen evolution reaction (OER) activity because of the presence of the U 5f-O 2p-Co 3d network. UCoO4 exhibits a low overpotential of 250 mV at 10 mA cm-2, surpassing other unitary cobalt-based catalysts ever reported. X-ray absorption spectroscopy revealed that the Co2+ ion in pristine UCoO4 was converted to high-valence Co3+/4+, while U6+ remained unchanged during the OER, indicating that only Co was the active site. Density functional theory calculations demonstrated that the OER activity of Co3+/4+ was synergistically enhanced by the covalent bonding of U6+-5f in the U 5f-O 2p-Co 3d network. This study opens new avenues for the realization of electronic structure manipulation via unique 5f involvement.
RESUMEN
In this study, n-type MoS2 monolayer flakes are grown through chemical vapor deposition (CVD), and a p-type Cu2O thin film is grown via electrochemical deposition. The crystal structure of the grown MoS2 flakes is analyzed through transmission electron microscopy. The monolayer structure of the MoS2 flakes is verified with Raman spectroscopy, multiphoton excitation microscopy, atomic force microscopy, and photoluminescence (PL) measurements. After the preliminary processing of the grown MoS2 flakes, the sample is then transferred onto a Cu2O thin film to complete a p-n heterogeneous structure. Data are confirmed via scanning electron microscopy, SHG, and Raman mapping measurements. The luminous energy gap between the two materials is examined through PL measurements. Results reveal that the thickness of the single-layer MoS2 film is 0.7 nm. PL mapping shows a micro signal generated at the 627 nm wavelength, which belongs to the B2 excitons of MoS2 and tends to increase gradually when it approaches 670 nm. Finally, the biosensor is used to detect lung cancer cell types in hydroplegia significantly reducing the current busy procedures and longer waiting time for detection. The results suggest that the fabricated sensor is highly sensitive to the change in the photocurrent with the number of each cell, the linear regression of the three cell types is as high as 99%. By measuring the slope of the photocurrent, we can identify the type of cells and the number of cells.
Asunto(s)
Técnicas Biosensibles , Neoplasias Pulmonares , Técnicas Biosensibles/métodos , Humanos , Neoplasias Pulmonares/diagnóstico , Microscopía Electrónica de Transmisión , Molibdeno/química , Espectrometría RamanRESUMEN
Herein, we have demonstrated the control over the structure of precatalysts to tune the properties of the active catalysts and their water oxidation activity. The reaction of K3 [Fe(CN)6 ] and Na2 [Fe(CN)5 (NO)] with Co(OH)2 @CC produced precatalysts PC-1 and PC-2, respectively, with distinct structural and electronic features. The replacement of the -CN group with strong π-acceptor -NO modulates the electronic and atomic structure of PC-2. As a result, a facile electrochemical transformation of PC-2 into active catalyst Fe-Co(OH)2 -Co(O)OH (AC-2) has been attained only in 15â CV cycles while 600â CV cycles are required for the electrochemical activation of PC-1 into AC-1. The X-ray absorption studies reveal the contraction of the Co-O and Fe-O bond in AC-2 because of the presence of a higher amount of Co3+ and Fe3+ than in AC-1. The high valent Co3+ and Fe3+ modulates the electronic properties of AC-2 and assists in the O-O bond formation, leading to the improved water oxidation activity.
RESUMEN
Fuel cells are considered as a promising alternative to the existing traditional energy systems towards a sustainable future. Nevertheless, the synthesis of efficient and robust platinum (Pt) based catalysts remains a challenge for practical applications. In this work, we present a simple and scalable molten-salt synthesis method for producing a low-platinum (Pt) nanoalloy implanted in metal-nitrogen-graphene. The as-prepared low-Pt alloyed graphene exhibits a high oxygen reduction activity of 1.29â A mgPt -1 and excellent durability over 30 000 potential cycles. The catalyst nanoarchitecture of graphene encased Pt nanoalloy provides a robust capability against nanoparticle migration and corrosion due to a strong metal-support interaction. Similarly, advanced characterization and theoretical calculations show that the multiple active sites in platinum alloyed graphene synergistically account for the improved oxygen reduction. This work not only provides an efficient and robust low-Pt catalyst but also a facile design idea and scalable preparation technique for integrated catalysts to achieve more profound applications in fuel cells and beyond.
RESUMEN
Single-atom nickel catalysts hold great promise for photocatalytic water splitting due to their plentiful active sites and cost-effectiveness. Herein, we adopt a reactive-group guided strategy to prepare atomically dispersed nickel catalysts on red phosphorus. The hydrothermal treatment of red phosphorus leads to the formation of P-H and P-OH groups, which behave as the reactive functionalities to generate the dual structure of single-atom P-Ni and P-O-Ni catalytic sites. The produced single-atom sites provide two different functions: P-Ni for water reduction and P-O-Ni for water oxidation. Benefitting from this specific Janus structure, Ni-red phosphorus shows an elevated hydrogen evolution rate compared to Ni nanoparticle-modified red phosphorus under visible-light irradiation. The hydrogen evolution rate was additionally enhanced with increased reaction temperature, reaching 91.51â µmol h-1 at 70 °C, corresponding to an apparent quantum efficiency of 8.9 % at 420â nm excitation wavelength.
RESUMEN
A Burkholderia gladioli strain, named BBB-01, was isolated from rice shoots based on the confrontation plate assay activity against several plant pathogenic fungi. The genome of this bacterial strain consists of two circular chromosomes and one plasmid with 8,201,484 base pairs in total. Pangenome analysis of 23 B. gladioli strains suggests that B. gladioli BBB-01 has the closest evolutionary relationship to B. gladioli pv. gladioli and B. gladioli pv. agaricicola. B. gladioli BBB-01 emitted dimethyl disulfide and 2,5-dimethylfuran when it was cultivated in lysogeny broth and potato dextrose broth, respectively. Dimethyl disulfide is a well-known pesticide, while the bioactivity of 2,5-dimethylfuran has not been reported. In this study, the inhibition activity of the vapor of these two compounds was examined against phytopathogenic fungi, including Magnaporthe oryzae, Gibberella fujikuroi, Sarocladium oryzae, Phellinus noxius and Colletotrichumfructicola, and human pathogen Candida albicans. In general, 2,5-dimethylfuran is more potent than dimethyl disulfide in suppressing the growth of the tested fungi, suggesting that 2,5-dimethylfuran is a potential fumigant to control plant fungal disease.
Asunto(s)
Antifúngicos/metabolismo , Antifúngicos/farmacología , Burkholderia gladioli/metabolismo , Compuestos Orgánicos Volátiles/metabolismo , Compuestos Orgánicos Volátiles/farmacología , Enfermedades de las Plantas/microbiología , Enfermedades de las Plantas/prevención & controlRESUMEN
The nitrogenous nucleophile electrooxidation reaction (NOR) plays a vital role in the degradation and transformation of available nitrogen. Focusing on the NOR mediated by the ß-Ni(OH)2 electrode, we decipher the transformation mechanism of the nitrogenous nucleophile. For the two-step NOR, proton-coupled electron transfer (PCET) is the bridge between electrocatalytic dehydrogenation from ß-Ni(OH)2 to ß-Ni(OH)O, and the spontaneous nucleophile dehydrogenative oxidation reaction. This theory can give a good explanation for hydrazine and primary amine oxidation reactions, but is insufficient for the urea oxidation reaction (UOR). Through operando tracing of bond rupture and formation processes during the UOR, as well as theoretical calculations, we propose a possible UOR mechanism whereby intramolecular coupling of the N-N bond, accompanied by PCET, hydration and rearrangement processes, results in high performance and ca. 100 % N2 selectivity. These discoveries clarify the evolution of nitrogenous molecules during the NOR, and they elucidate fundamental aspects of electrocatalysis involving nitrogen-containing species.
RESUMEN
The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure-activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO-Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH⢠first for VO-Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co-OOHâ¢. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.
RESUMEN
BACKGROUND/PURPOSE: Enteral feeding, mainly by using a nasogastric tube (NGT), is generally favored over parenteral supplementation in head and neck cancer (HNC) patients with dysphagia. However, the placement of a NGT, either blindly or by endoscopy, is technically challenging in these patients due to the obstructive mass and the altered regional anatomy. The aim of this retrospective study was to estimate the clinical feasibility and safety of fluoroscopic-guided NGT placement in patients with advanced HNC. METHODS: Between January 2010 and June 2018, a total of 572 fluoroscopic-guided NGT placements were performed on 231 patients. Technical success was defined as successful insertion of the NGT into the stomach with proper positioning, which was verified by air injection into the NGT. Complications, including aspiration pneumonia, and the ones requiring intensive care, or procedure-related death, were recorded. RESULTS: Technical success was obtained in 558 (97.6%) procedures, and the other 14 (2.4%) procedures failed because of patient intolerance (n = 1) and high-grade obstruction (n = 13). Of the high-grade obstruction patients, eight (61.5%) were shifted to percutaneous radiological gastrostomy, two (15.4%) to surgical feeding jejunostomy, one (7.6%) to endoscopic balloon dilatation, and two (15.4%) to orogastric tube insertion. The average procedure time and fluoroscopy time were 11.7 ± 7.4 min and 3.1 ± 3.1 min, respectively. There were no major complications. CONCLUSION: Our results show that fluoroscopic-guided NGT placement is a highly safe and effective procedure for patients with advanced HNC requiring enteral feeding.