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2.
Acc Chem Res ; 2024 Feb 09.
Artículo en Inglés | MEDLINE | ID: mdl-38334075

RESUMEN

ConspectusMetal nanoparticles (NPs) are one of the most frequently used heterogeneous catalysts. However, only the surface atoms in the NPs can participate in catalytic reactions. To maximize the atomic efficiency, the active sites can be reduced to single atoms. Generally, catalysts that have isolated metal atoms on the surface of a support are called single-atom catalysts (SACs). Many techniques have been developed and applied to probe the structures of SACs. Nevertheless, the structural characterization of SACs is still challenging as it requires the analysis of their structure and properties with atomic and sometimes even subatomic resolution. X-ray absorption spectroscopy (XAS) is a powerful tool in investigating the local coordination environment of SACs since it is element-specific and can provide accurate structural information at the subatomic level (∼0.01 Å).In this Account, we present our perspectives on the structural analysis of SACs from some unique features in the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). We first highlight the importance of the XANES peak features in the sensitive analysis of SAC structures. Such analysis is illustrated to be even more useful in the joint applications of experimental and theoretical XAS. The inspection of the metal-metal (M-M) peak in Fourier transformed EXAFS (FT-EXAFS) spectra is a widely used method to identify the single-atom structure, but this method is not always reliable. Thus, we point out the importance of fitting EXAFS and the thorough interpretation of structural parameters such as coordination numbers (CNs, the number of neighboring atoms next to a chosen atom), bond distances, and the Debye-Waller factor (σ2). The small FT-EXAFS peak for the M-M shell is often ignored in the structural analysis of SACs. Here, it is demonstrated that a careful analysis of these small peaks could help more reliably analyze the SAC structure, and it would be particularly useful in the analysis of a single-atom alloy (SAA). Next, the usefulness of bond distance and σ2 analysis is highlighted, and such analysis is shown to be particularly helpful for the analysis of SAAs, which is rarely discussed in the literature. Given the advantage that XAS data can be collected under various conditions, we show that in situ XAS can provide important information about the catalytic mechanism of the SAC catalyst. In particular, we emphasize the significance of using an advanced in situ technique to extract detailed structural information that is difficult to obtain from regular XAS experiments. Finally, we highlight the importance of jointly using XAS with other complementary methods in a more complete understanding of the structure and properties of SACs. It is anticipated that with further development of XAS techniques and improved data analysis, XAS will become even more powerful in providing insights into the structure-property relationships of SACs, which can advance their practical applications.

3.
Abdom Radiol (NY) ; 2024 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-38411693

RESUMEN

Gallbladder (GB) polyps are a common incidental finding on sonography, but only a small fraction of polyps become GB cancer. The Society of Radiologists in Ultrasound (SRU) consensus committee recently performed an extensive literature review and published guidelines for GB polyp follow-up/management to provide clarity among the many heterogeneous recommendations that are available to clinicians. As these guidelines have become adopted into clinical practice, challenging clinical scenarios have arisen including GB polyps in primary sclerosing cholangitis (PSC), high risk geographic/genetic patient populations, shrinking polyps, pedunculated vs sessile polyps, thin vs thick stalked polyps, vascular polyps and multiple polyps. According to the SRU guidelines, clinicians should refer to gastroenterology guidelines when managing GB polyps in patients with known PSC. If patients at high geographic/genetic risk develop GB polyps, 'extremely low risk' polyps may be managed as 'low risk' and 10-14 mm 'extremely low risk' or '7-14 mm' low risk polyps that decrease in size by ≥ 4 mm require no follow-up. Thin-stalked or pedunculated polyps are 'extremely low risk' and thick-stalked pedunculated polyps are 'low risk'. Sessile polyps are 'low risk' but should receive immediate specialist referral if features suggestive of GB cancer are present. Neither polyp multiplicity nor vascularity impact risk of GB cancer and follow up should be based on morphology alone.

4.
Trop Med Infect Dis ; 9(1)2024 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-38251216

RESUMEN

Despite over two decades of progress against HIV/AIDS in adjacent sub-Saharan Africa, HIV rates and deaths due to AIDS are exponentially rising in Madagascar. Furthermore, a growing body of evidence suggests that, due to a scarcity of general-population screening data, even the startling increase demonstrated by official models vastly underestimates the true population prevalence of HIV. We aimed to implement a real-world HIV screening and treatment protocol to serve a general population stemming from across northern Madagascar. In collaboration with the Malagasy Ministry of Health, we provided point-of-care HIV screening and confirmatory testing for over 1000 participants from 73 towns, villages, and cities. We recorded an overall HIV prevalence of 2.94%. Notably, we observed a 13.1% HIV prevalence rate among urban populations and showed that proximity to a major route of travel was significantly associated with HIV risk. We also observed a link between HIV risk and various occupations, including those associated with increased mobility (such as mining). Importantly, all HIV-positive individuals were initiated on antiretroviral therapy in concordance with local health authorities. To our knowledge, this study marks the largest primary test data-based HIV study to date among Madagascar's general population, showing a greatly higher HIV prevalence (2.9%) than previously reported modeling-based figures (0.4%). Our rates aligned with the pattern of higher prevalence demonstrated in smaller general-population screening studies occurring more commonly prior to political strife in the mid-2000s. These findings demonstrate evidence of a growing HIV epidemic in northern Madagascar and underscore the need for future investment into more comprehensive HIV screening and control initiatives in Madagascar.

5.
Sensors (Basel) ; 23(22)2023 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-38005577

RESUMEN

Monitoring marine fauna is essential for mitigating the effects of disturbances in the marine environment, as well as reducing the risk of negative interactions between humans and marine life. Drone-based aerial surveys have become popular for detecting and estimating the abundance of large marine fauna. However, sightability errors, which affect detection reliability, are still apparent. This study tested the utility of spectral filtering for improving the reliability of marine fauna detections from drone-based monitoring. A series of drone-based survey flights were conducted using three identical RGB (red-green-blue channel) cameras with treatments: (i) control (RGB), (ii) spectrally filtered with a narrow 'green' bandpass filter (transmission between 525 and 550 nm), and, (iii) spectrally filtered with a polarising filter. Video data from nine flights comprising dolphin groups were analysed using a machine learning approach, whereby ground-truth detections were manually created and compared to AI-generated detections. The results showed that spectral filtering decreased the reliability of detecting submerged fauna compared to standard unfiltered RGB cameras. Although the majority of visible contrast between a submerged marine animal and surrounding seawater (in our study, sites along coastal beaches in eastern Australia) is known to occur between 515-554 nm, isolating the colour input to an RGB sensor does not improve detection reliability due to a decrease in the signal to noise ratio, which affects the reliability of detections.


Asunto(s)
Agua de Mar , Dispositivos Aéreos No Tripulados , Animales , Humanos , Reproducibilidad de los Resultados , Australia
6.
Cancer Lett ; 552: 215958, 2023 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-36252816

RESUMEN

Since lung cancer remains the leading cause of cancer death globally, there is an urgent demand for novel therapeutic targets. We carried out a CRISPR interference (CRISPRi) loss-of-function screen for human lung adenocarcinoma (LUAD) targeting 2098 deregulated genes using a customized algorithm to comprehensively probe the functionality of every resolvable transcriptional start site (TSS). CASP8AP2 was identified as the only hit that significantly affected the viability of all eight screened LUAD cell lines while the viability of non-transformed lung cells was only moderately impacted. Knockdown (KD) of CASP8AP2 induced both autophagy and apoptotic cell death pathways. Systematic expression profiling linked the AP-1 transcription factor to the CASP8AP2 KD-induced cancer cell death. Furthermore, inhibition of AP-1 reverted the CASP8AP2 silencing-induced phenotype. Overall, the tailored CRISPRi screen profiled the impact of over 2000 genes on the survival of eight LUAD cell lines and identified the CASP8AP2 - AP-1 axis mediating lung cancer viability.


Asunto(s)
Adenocarcinoma del Pulmón , Proteínas Reguladoras de la Apoptosis , Proteínas de Unión al Calcio , Neoplasias Pulmonares , Humanos , Adenocarcinoma del Pulmón/genética , Adenocarcinoma del Pulmón/metabolismo , Apoptosis/genética , Repeticiones Palindrómicas Cortas Agrupadas y Regularmente Espaciadas , Detección Precoz del Cáncer , Pulmón/patología , Neoplasias Pulmonares/metabolismo , Factor de Transcripción AP-1/genética , Factor de Transcripción AP-1/metabolismo , Proteínas Reguladoras de la Apoptosis/genética , Proteínas Reguladoras de la Apoptosis/metabolismo , Proteínas de Unión al Calcio/genética , Proteínas de Unión al Calcio/metabolismo
8.
Behav Sci (Basel) ; 12(8)2022 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-35892350

RESUMEN

Facial expressions play a key role in interpersonal communication when it comes to negotiating our emotions and intentions, as well as interpreting those of others. Research has shown that we can connect to other people better when we exhibit signs of empathy and facial mimicry. However, the relationship between empathy and facial mimicry is still debated. Among the factors contributing to the difference in results across existing studies is the use of different instruments for measuring both empathy and facial mimicry, as well as often ignoring the differences across various demographic groups. This study first looks at the differences in the empathetic abilities of people across different demographic groups based on gender, ethnicity and age. The empathetic ability is measured based on the Empathy Quotient, capturing a balanced representation of both emotional and cognitive empathy. Using statistical and machine learning methods, this study then investigates the correlation between the empathetic ability and facial mimicry of subjects in response to images portraying different emotions displayed on a computer screen. Unlike the existing studies measuring facial mimicry using electromyography, this study employs a technology detecting facial expressions based on video capture and deep learning. This choice was made in the context of increased online communication during and after the COVID-19 pandemic. The results of this study confirm the previously reported difference in the empathetic ability between females and males. However, no significant difference in empathetic ability was found across different age and ethnic groups. Furthermore, no strong correlation was found between empathy and facial reactions to faces portraying different emotions shown on a computer screen. Overall, the results of this study can be used to inform the design of online communication technologies and tools for training empathy team leaders, educators, social and healthcare providers.

9.
Radiology ; 305(2): 277-289, 2022 11.
Artículo en Inglés | MEDLINE | ID: mdl-35787200

RESUMEN

Gallbladder polyps (also known as polypoid lesions of the gallbladder) are a common incidental finding. The vast majority of gallbladder polyps smaller than 10 mm are not true neoplastic polyps but are benign cholesterol polyps with no inherent risk of malignancy. In addition, recent studies have shown that the overall risk of gallbladder cancer is not increased in patients with small gallbladder polyps, calling into question the rationale for frequent and prolonged follow-up of these common lesions. In 2021, a Society of Radiologists in Ultrasound, or SRU, consensus conference was convened to provide recommendations for the management of incidentally detected gallbladder polyps at US. See also the editorial by Sidhu and Rafailidis in this issue.


Asunto(s)
Enfermedades de la Vesícula Biliar , Neoplasias de la Vesícula Biliar , Neoplasias Gastrointestinales , Pólipos , Humanos , Enfermedades de la Vesícula Biliar/diagnóstico por imagen , Pólipos/diagnóstico por imagen , Pólipos/patología , Neoplasias de la Vesícula Biliar/diagnóstico por imagen , Neoplasias de la Vesícula Biliar/patología , Radiólogos
10.
Sport Sci Health ; 18(4): 1475-1481, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35669926

RESUMEN

The COVID-19 outbreak presents a serious health challenges, with Australia enforcing tight restrictions, impacting sporting activities and sleep health of many Australians. Routine lifestyle patterns (physical activity and employment) are important to maintaining overall sleep health. Current literature indicates COVID-19 pandemic negatively affected the employment status and sport engagement. The aim of this study was to explore the effect of physical activity during COVID-19 on sleep health, and its association with employment and sport engagement of community-level athletes throughout Australia. Participants self-reported sleep health prior to COVID-19 (pre-sleep) and over the month prior to data collection (during-sleep) using the validated 5-item Satisfaction Alertness Timing Efficiency and Duration questionnaire (SATED). Wilcoxon Signed Rank Test assessed the difference in pre- and during perceived sleep health scores. A generalized linear model was used to assess the impact of sporting and demographic factors on a community athlete's change in perceived sleep health score. A total of 139 community-level Australian athletes responded. The majority of participants were aged 18-30 and engaged in full-time employment prior to COVID-19 (n = 82, 54%). Eight percent of participants were unemployed prior to the COVID-19 pandemic (n = 12, 8%). Our findings show that sleep health values were higher during COVID-19, with 91.4% of respondents able to maintain some form of physical activity during the pandemic. Together, our results show better sleep health scores reported by the respondents who maintained or lost employment and maintained sporting engagements during the pandemic.

11.
Ultrasound Q ; 38(2): 96-102, 2022 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-35221317

RESUMEN

ABSTRACT: Gallbladder polyps (GPs) are a common incidental finding on ultrasound; however, important differences in recommended management exist among professional society guidelines.An electronic survey was sent to 189 fellows of the Society of Radiologists in Ultrasound. Main outcomes included preferences and current practice patterns for evaluation, management, and surveillance of GPs as well as personal lifetime experience with gallbladder sonography and GPs.A total of 64 subjects (34%) with experience in gallbladder sonography completed the study. The estimated combined total number of gallbladder scans seen by the responders was 3,071,880. None of fellows had ever seen a pedunculated GP <1 cm detected on ultrasound that was proven to be malignant at the time of detection or during subsequent follow-up. All of the fellows used size as a feature to stratify recommendations. The median size threshold currently used by Society of Radiologists in Ultrasound fellows for recommending ultrasound follow-up was 6 mm, and their preferred threshold was 7 mm. The median size threshold for recommending surgical consultation was 10 mm, and the preferred threshold was 10 mm. Wall thickening and shape were considered important factors by 76% and 67% of respondents, respectively.Society of Radiologists in Ultrasound fellows tend to provide recommendations most similar to the American College of Radiology and Canadian Association of Radiology guidelines for management of GPs. Many would prefer guidelines that result in fewer recommendations for follow-up and surgical consultation. Despite a substantial combined experience, this survey did not uncover any case of a small GP that was malignant.


Asunto(s)
Vesícula Biliar , Pólipos , Canadá , Vesícula Biliar/diagnóstico por imagen , Humanos , Hallazgos Incidentales , Radiólogos , Encuestas y Cuestionarios
12.
AJR Am J Roentgenol ; 218(3): 472-483, 2022 03.
Artículo en Inglés | MEDLINE | ID: mdl-34549608

RESUMEN

BACKGROUND. Previous European multisociety guidelines recommend routine follow-up imaging of gallbladder polyps (including polyps < 6 mm in patients without risk factors) and cholecystectomy for polyp size changes of 2 mm or more. OBJECTIVE. The purpose of this study was to assess longitudinal changes in the number and size of gallbladder polyps on serial ultrasound examinations. METHODS. This retrospective study included patients who underwent at least one ultrasound examination between January 1, 2010, and December 31, 2020 (as part of a hepatocellular carcinoma screening and surveillance program) that showed a gallbladder polyp. Number of polyps and size of largest polyp were recorded based primarily on review of examination reports. Longitudinal changes on serial examinations were summarized. Pathologic findings from cholecystectomy were reviewed. RESULTS. Among 9683 patients, 759 (8%) had at least one ultrasound examination showing a polyp. Of these, 434 patients (248 men, 186 women; mean age, 50.6 years) had multiple examinations (range, 2-19 examinations; mean, 4.8 examinations per patient; mean interval between first and last examinations, 3.6 ± 3.1 [SD] years; maximum interval, 11.0 years). Among these 434 patients, 257 had one polyp, 40 had two polyps, and 137 had more than two polyps. Polyp size was 6 mm or less in 368 patients, 7-9 mm in 52 patients, and 10 mm or more in 14 patients. Number of polyps increased in 9% of patients, decreased in 14%, both increased and decreased on serial examinations in 22%, and showed no change in 55%. Polyp size increased in 10% of patients, decreased in 16%, both increased and decreased on serial examinations in 18%, and showed no change in 56%. In 9% of patients, gallbladder polyps were not detected on follow-up imaging; in 6% of patients, gallbladder polyps were not detected on a follow-up examination but were then detected on later studies. No gallbladder carcinoma was identified in 19 patients who underwent cholecystectomy. CONCLUSION. Gallbladder polyps fluctuate in size, number, and visibility over serial examinations. Using a 2-mm threshold for growth, 10% increased in size. No carcinoma was identified. CLINICAL IMPACT. European multisociety guidelines that propose surveillance of essentially all polyps and a 2-mm size change as the basis for cholecystectomy are likely too conservative for clinical application.


Asunto(s)
Enfermedades de la Vesícula Biliar/diagnóstico por imagen , Hallazgos Incidentales , Pólipos/diagnóstico por imagen , Ultrasonografía/métodos , Femenino , Vesícula Biliar/diagnóstico por imagen , Humanos , Masculino , Persona de Mediana Edad , Estudios Retrospectivos
13.
Temperature (Austin) ; 8(4): 372-380, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-34901319

RESUMEN

We investigate the effects of seasonal heat stress on cognitive function in outdoor workers. Thirty-nine workers from an oil and gas industry in the Middle-East volunteered for cognitive testing before (5.30 to 7.00 am) and after (3.30 to 5.00 pm) their daily work-shift in hot (August - average daily temperature: ~41°C) and temperate (January - average daily temperature: ~22°C) seasons. While physical activity was reduced in hot compared to temperate season (average normalized acceleration: 96 ± 33 vs. 112 ± 31 × 10-3 g; -12.5 ± 4.7%; P = 0.010), the average core temperature during the work-shift was higher in the hot season (37.4 ± 0.2 vs. 37.2 ± 0.2°C; P = 0.002). Peak core temperature was 38.0 ± 0.1°C and 37.8 ± 0.1°C in hot and temperate seasons, respectively. Cognitive performance did not differ between seasons for tests of recognition memory (P = 0.169), working memory (P = 0.797) and executive function (P = 0.145), independent of testing time. Whereas there was no significant main effect of testing time for tests of recognition memory (P = 0.503) and working memory (P = 0.849), the number of problems solved on the first choice for the executive function test was lower in the afternoon than the morning (-9.2 ± 5.3%; P = 0.039). There was no season × testing time interaction for any cognitive tests (P ≥ 0.145). In the absence of hyperthermia, living and working in a hot environment does not alter cognitive function in oil and gas industry workers tested in a quiet and temperature-controlled room, with reduced clothing encumbrance (relative to work). Conclusions should not be extrapolated to more stressful situations (i.e., thermal stressor present, pronounced dehydration, noise).

14.
Small ; 17(27): e2005162, 2021 07.
Artículo en Inglés | MEDLINE | ID: mdl-33511737

RESUMEN

Silver nanoclusters (NCs) are of significant interest owing to their interesting structural, electronic, and catalytic properties. Among these NCs, Ag25 (SR)18 is particularly attractive due to its identical geometry as its Au counterpart, Au25 (SR)18 . Herein, the site-specific electronic properties of Ag25 (SR)18 and Au25 (SR)18 using X-ray spectroscopy experiments and quantum simulations are presented. To overcome the final state effect observed in X-ray photoelectron spectroscopy (XPS), a unique method is developed to reliably analyze the charge transfer behavior of the NCs. Density functional theory calculations are combined with XPS to provide more insight into the electronic properties of the NCs. The differences in the XPS valence bands of these two NCs are further compared and interpreted using the relativistic effect. The first derivative of the X-ray absorption near-edge structure (XANES) spectrum is further used as a tool to sensitively probe the bonding properties of Ag25 (SR)18 . By combining the experimental XANES data and their site-specific quantum simulations, the large impact of the staple motif on the bonding properties of the NC is demonstrated. These findings highlight the unique electronic properties of each atomic site in Ag25 (SR)18 ; the effective X-ray analysis techniques developed here can offer new opportunities for the site-specific study of other NCs.


Asunto(s)
Oro , Plata , Electrónica , Espectroscopía de Fotoelectrones , Rayos X
15.
J Phys Chem Lett ; 12(1): 257-275, 2021 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-33332974

RESUMEN

Thiolate-protected metal nanoclusters, which are smaller than 2 nm and have a specific number of metal atoms, have been greatly investigated in areas such as catalysis, sensing, and energy conversion because of their unique chemical, optical, structural, and electronic properties. Doping monometallic nanoclusters with another metal offers the opportunity to enhance these properties even further. The atomic structure of thiolate-protected bimetallic nanoclusters has been thoroughly studied using various X-ray methods, but the electronic structures of these complexes are often under-discussed. This Perspective summarizes works examining the electronic properties (charge states and energy levels) of these materials using density functional theory, square-wave voltammetry, UV-vis spectroscopy, and X-ray photoelectron spectroscopy. This information is then related to the catalytic activities of these complexes in various representative reactions (e.g., carbon-carbon coupling, hydrogenation, and oxidation). The significance of the structure-property relationship between the electronic properties and the catalytic performance of thiolate-protected bimetallic nanoclusters is demonstrated.

16.
Chem Soc Rev ; 50(1): 569-588, 2021 Jan 07.
Artículo en Inglés | MEDLINE | ID: mdl-33170202

RESUMEN

Monometallic catalysts, in particular those containing noble metals, are frequently used in heterogeneous catalysis, but they are expensive, rare and the ability to tailor their structures and properties remains limited. Traditionally, alloy catalysts have been used instead that feature enhanced electronic and chemical properties at a reduced cost. Furthermore, the introduction of single metal atoms anchored onto supports provided another effective strategy to increase both the atomic efficiency and the chance of tailoring the properties. Most recently, single-atom alloy catalysts have been developed in which one metal is atomically dispersed throughout the catalyst via alloy bonding; such catalysts combine the traditional advantages of alloy catalysts with the new feature of tailoring properties achievable with single atom catalysts. This review will first outline the atomic scale structural analysis on single-atom alloys using microscopy and spectroscopy tools, such as high-angle annular dark field imaging-scanning transmission electron microscopy and extended X-ray absorption fine structure spectroscopy. Next, progress in research to understand the electronic properties of single-atom alloys using X-ray spectroscopy techniques and quantum calculations will be presented. The catalytic activities of single-atom alloys in a few representative reactions will be further discussed to demonstrate their structure-property relationships. Finally, future perspectives for single-atom alloy catalysts from the structural, electronic and reactivity aspects will be proposed.

17.
Nanoscale ; 12(33): 17245-17252, 2020 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-32808949

RESUMEN

TiO2 is one of the most widely used photocatalysts and photothermocatalysts. Tailoring their structure and electronic properties is crucial for the design of high-performance TiO2 catalysts. Herein, we report a strategy to significantly enhance the performance of TiO2 in the photothermocatalytic reduction of CO2 by doping high crystalline nano-TiO2 with tungsten. A variety of tungsten doping concentrations ranging from 2% to 10% were tested and they all showed enhanced catalytic activities. The 4% W-doped TiO2 exhibited the highest activity, which was 3.5 times greater than that of the undoped TiO2 reference. Structural characterization of these W-doped TiO2 catalysts indicated that W was successfully doped into the TiO2 lattice at relatively low dopant concentration. Synchrotron X-ray absorption spectroscopy at both the W L3- and Ti K-edges was further used to provide insight into the local structure and bonding properties of the catalysts. It was found that the replacement of Ti with W led to the formation of Ti vacancies in order to maintain the charge neutrality. Consequently, dangling oxygen and oxygen vacancies were produced that acted as catalytically active sites for the CO2 reduction. As the W doping concentration increased from 2% to 4%, more such active sites were generated which thus resulted in the enhancement of the catalytic activity. When the W doping concentration was further increased to 10%, the extra W species that cannot replace the Ti in the lattice aggregated to form WO3. Due to the lower conduction band of WO3, the catalytic O sites were deactivated and CO2 reduction was inhibited. This work presents a useful strategy for the development of highly efficient catalysts for CO2 reduction as well as new insights into the catalytic mechanism in cation-doped TiO2 photothermocatalysis.

18.
Adv Mater ; 32(44): e2002910, 2020 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-32656812

RESUMEN

Single-atom catalysts (SACs) have recently emerged as an exciting system in heterogeneous catalysis showing outstanding performance in many catalytic reactions. Single-atom catalytic sites alone are not stable and thus require stabilization from substrates. Crystalline porous materials such as zeolites and metal-organic frameworks (MOFs) are excellent substrates for SACs, offering high stability with the potential to further enhance their performance due to synergistic effects. This review features recent work on the structure, electronic, and catalytic properties of zeolite and MOF-protected SACs, offering atomic-scale views from the "inside" thanks to the subatomic resolution of synchrotron X-ray absorption spectroscopy (XAS). The extended X-ray absorption fine structure and associated methods will be shown to be powerful tools in identifying the single-atom site and can provide details into the coordination environment and bonding disorder of SACs. The X-ray absorption near-edge structure will be demonstrated as a valuable method in probing the electronic properties of SACs by analyzing the white line intensity, absorption edge shift, and pre-/postedge features. Emphasis is also placed on in situ/operando XAS using state-of-the-art equipment, which can unveil the changes in structure and properties of SACs during the dynamic catalytic processes in a highly sensitive and time-resolved manner.

19.
J Neurophysiol ; 123(5): 1896-1906, 2020 05 01.
Artículo en Inglés | MEDLINE | ID: mdl-32267196

RESUMEN

This study investigated whether modulation of corticospinal-motoneuronal excitability and/or synaptic transmission of the Ia afferent spinal reflex contributes to decreases in voluntary activation and muscular force after an acute bout of prolonged static muscle stretching. Fifteen men performed five 60-s constant-torque stretches (15-s rest intervals; total duration 5 min) of the plantar flexors on an isokinetic dynamometer and a nonstretching control condition in random order on 2 separate days. Maximum isometric plantar flexor torque and triceps surae muscle electromyographic activity (normalized to M wave; EMG/M) were simultaneously recorded immediately before and after each condition. Motor-evoked potentials (using transcranial magnetic stimulation) and H-reflexes were recorded from soleus during EMG-controlled submaximal contractions (23.4 ± 6.9% EMG maximum). No changes were detected in the control condition. After stretching, however, peak torque (mean ± SD; -14.3 ± 7.0%) and soleus EMG/M (-17.8 ± 6.2%) decreased, and these changes were highly correlated (r = 0.83). No changes were observed after stretching in soleus MEP or H-reflex amplitudes measured during submaximal contractions, and interindividual variability of changes was not correlated with changes in EMG activity or maximum torque. During EMG-controlled submaximal contractions, torque production was significantly decreased after stretching (-22.7 ± 15.0%), indicating a compromised muscular output. These data provide support that changes in the excitability of the corticospinal-motoneuronal and Ia afferent spinal reflex pathways do not contribute to poststretch neural impairment.NEW & NOTEWORTHY This study is the first to specifically examine potential sites underlying the decreases in neural activation of muscle and force production after a bout of muscle stretching. However, no changes were found in either the H-reflex or motor-evoked potential amplitude during submaximal contractions.


Asunto(s)
Vías Aferentes/fisiología , Fenómenos Biomecánicos/fisiología , Potenciales Evocados Motores/fisiología , Reflejo H/fisiología , Neuronas Motoras/fisiología , Contracción Muscular/fisiología , Músculo Esquelético/fisiología , Adulto , Electromiografía , Humanos , Masculino , Estimulación Magnética Transcraneal , Adulto Joven
20.
J Phys Chem Lett ; 11(6): 2219-2229, 2020 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-32109069

RESUMEN

CO oxidation is one of the most studied reactions in heterogeneous catalysis. It is present in air cleaning and automotive emission control. It also participates in the removal of CO from streams of hydrogen used in fuel cells. Because of the competitive adsorption of CO and O2 over active sites, the use of Pt-based catalysts for low-temperature CO oxidation remains a challenge. Recently, great progress has been made with catalysts containing Pt-Fe species because of the contribution of Fe species to O2 activation. The structure-activity relationship and reaction mechanisms have been investigated with various Pt-Fe catalysts. In this Perspective, we give a summary of the recent advances of low-temperature CO oxidation over Pt-Fe catalysts with a focus on the synergistic effect of Pt and Fe species in the CO and O2 activation of catalytic reactions. Future prospects for the preparation of highly effective Pt-Fe catalysts are also proposed.

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