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A Gram-stain-negative, red pigment-producing, aerobic, and rod-shaped bacterial strain (A2-2T) was isolated from a bleached scleractinian coral (Porites lutea). Strain A2-2T grew with 1.0-7.0â% (w/v) NaCl (optimum, 3.0â%), at pH 6.0-11.0 (optimum, pH 8.0), and at 18-41â°C (optimum, 35â°C). Results of phylogenetic analysis based on 16S rRNA gene sequences suggested that strain A2-2T fell within the genus Spartinivicinus and was closely related to Spartinivicinus ruber S2-4-1HT (98.1â% sequence similarity) and Spartinivicinus marinus SM1973T (98.0â% sequence similarity). The predominant cellular fatty acids of strain A2-2T were C16â:â0 (31.0â%), summed feature 3 (29.0â%), summed feature 8 (11.7â%), C12â:â0 3-OH (6.4â%), and C10â:â0 3-OH (5.5â%), while the major respiratory quinone was Q-9. The polar lipids mainly comprised phosphatidylethanolamine, phosphatidylglycerol, diphosphatidylglycerol, and an unidentified phospholipid. The genome size of strain A2-2T was 6.8 Mb, with a G+C content of 40.2âmol%. The DNA-DNA hybridization value was 24.2â% between A2-2T and S. ruber S2-4-1HT and 36.9â% between A2-2T and S. marinus SM1973T, while the average nucleotide identity values were 80.1 and 88.8â%, respectively. Based on these findings, strain A2-2T could be recognized to represent a novel species of the genus Spartinivicinus, for which the name Spartinivicinus poritis sp. nov. is proposed. The type strain is A2-2T (=MCCC 1K08228T=KCTC 8323T).
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Antozoários , Técnicas de Tipagem Bacteriana , Composição de Bases , DNA Bacteriano , Ácidos Graxos , Filogenia , Pigmentos Biológicos , RNA Ribossômico 16S , Análise de Sequência de DNA , RNA Ribossômico 16S/genética , Animais , Antozoários/microbiologia , DNA Bacteriano/genética , Pigmentos Biológicos/metabolismo , Hibridização de Ácido Nucleico , FosfolipídeosRESUMO
PCDD/Fs are dioxins produced by waste incineration and pose risks to human health. We aimed to detail the health risks of airborne and soil PCDD/Fs near a municipal solid-waste incinerator (MSWI) for the surrounding population and develop a new model that improves upon existing methods. Thus, we conducted field sampling and then investigated a MSWI in the Pearl River Delta (2016-2018). Our results showed that the carcinogenic and non-carcinogenic risk values of PCDD/Fs exposed to residents in nearby areas were acceptable, with hazard index (HI) values lower than 1.0 and a total carcinogenic risk lower than 1.0E-6. Notably, the results raised concerns regarding higher non-carcinogenic risks in children than in adults. Comparative analysis of the frequency accumulation diagram, accumulated probability risk, and the absolute value of error (δ) between the 95% confidence interval (CI) and the 90% CI of the Monte Carlo stochastic simulation-triangular fuzzy number (MCSS-TFN) and the MCSS model, respectively, demonstrated that the MCSS-TFN exhibited less uncertainty than the MCSS model, regardless of the health risk value of PCDD/Fs in ambient air or in soil. This observation underscores the superiority of the MCSS-TFN model over other models in assessing the health risks associated with PCDD/Fs in situations with limited data. Our new method overcomes the limited dataset size and high uncertainty in assessing the health risks of dioxin substances, providing a more comprehensive understanding of their associated health risks than MCSS models.
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Poluentes Atmosféricos , Dioxinas , Dibenzodioxinas Policloradas , Adulto , Criança , Humanos , Resíduos Sólidos , Monitoramento Ambiental/métodos , Dibenzodioxinas Policloradas/toxicidade , Dibenzodioxinas Policloradas/análise , Dibenzofuranos , Poluentes Atmosféricos/análise , Incineração , Dioxinas/toxicidade , Medição de Risco , Dibenzofuranos Policlorados/análise , SoloRESUMO
Synthetic supramolecular transmembrane anionophores have emerged as promising anticancer chemotherapeutics. However, key to their targeted application is achieving spatiotemporally controlled activity. Herein, we report a series of chalcogen-bonding diaryl tellurium-based transporters in which their anion binding potency and anionophoric activity are controlled through reversible redox cycling between Te oxidation states. This unprecedented in situ reversible multistate switching allows for switching between ON and OFF anion transport and is crucially achieved with biomimetic chemical redox couples.
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A Gram-stain-negative, aerobic, rod-shaped, nonmotile and yellow-pigmented bacterium designated E7-10T was isolated from a bleached scleractinian coral Porites lutea. Strain E7-10T grew with 1.0-8.0â% (w/v) NaCl (optimum, 4.0â%), at 18-41â°C (optimum, 28â°C) and at pH 6.0-10.0 (optimum, pH 8.0). Phylogenetic analysis using 16S rRNA gene sequences revealed that E7-10T formed a lineage within the genus Hoeflea, but it was distinct from the closest species 'Hoeflea prorocentri' PM5-8T, showing 98.01â% sequence similarity. The predominant cellular fatty acids of E7-10T were summed feature 8 (26.7â%), C18â:â1 ω7c 11-methyl (26.2â%), C16â:â0 (20.8â%) and C19â:â0 cyclo ω8c (17.9â%). The major respiratory quinone was Q-10. The polar lipids mainly comprised phosphatidylethanolamine, two glycolipids and five phospholipids. The genome size of E7-10T was 5.58 Mb with G+C content 60.27 mol%. The digital DNA-DNA hybridization and average nucleotide identity values between the genomes of strains E7-10T and PM5-8T were 19.50 and 75.95â%, respectively, which were both below the defined cutoff values (70â% and 95-96â%, respectively) for species delimitation. Thus, strain E7-10T represents a novel species within the genus Hoeflea, for which the name Hoeflea poritis sp. nov. is proposed. The type strain is E7-10T (=JCM 35852T=MCCC 1K08229T).
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Antozoários , Phyllobacteriaceae , Animais , Ácidos Graxos/química , Filogenia , RNA Ribossômico 16S/genética , Técnicas de Tipagem Bacteriana , Ubiquinona/química , Composição de Bases , DNA Bacteriano/genética , Análise de Sequência de DNA , Fosfolipídeos/químicaRESUMO
BACKGROUND: Positron emission tomography (PET) imaging with radiolabeled fibroblasts activation protein inhibitor (FAPI) provides the opportunity to directly visualize fibrosis. This study aimed to investigate the feasibility of 68Ga-FAPI PET imaging in assessing right ventricular (RV) fibrotic remodeling and the relationship between FAPI uptake with parameters of pulmonary hemodynamics and cardiac function in pulmonary arterial hypertension (PAH) patients. METHODS: In this pilot study, sixteen PAH patients were enrolled to participate in cardiac 68Ga-FAPI PET/CT imaging. All patients underwent right heart catheterization and echocardiography for assessment of pulmonary hemodynamics and cardiac function within seven days. Cardiac FAPI uptake was visually assessed and quantified as maximum standardized uptake value (SUVmax). RESULTS: Twelve PAH patients exhibited FAPI uptake in RV free wall and insertion point. The overall activity of FAPI accumulated in the RV free wall (SUVmax: 2.5 ± 1.8, P < 0.001) and insertion point (SUVmax:2.5 ± 1.7, P < 0.001) was significantly upregulated compared to left ventricle (SUVmax:1.5 ± 0.5). Patients with tricuspid annular plane systolic excursion (TAPSE) < 17 mm presented significantly higher uptake than those with TAPSE ≥ 17 mm in both RV free wall (SUVmax: 3.4 ± 1.9 vs 1.7 ± 1.1, P = 0.010) and insertion point (SUVmax: 3.4 ± 1.9 vs 1.6 ± 0.7, P = 0.028), indicating RV uptake of FAPI was associated with RV dysfunction. There was significant positive correlation between cardiac FAPI uptake and total pulmonary resistance and the level of N-terminal pro b-type natriuretic peptide. CONCLUSIONS: 68Ga-FAPI PET/CT imaging is feasible to directly visualize fibrotic remodeling of RV in patients with PAH.
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Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada , Hipertensão Arterial Pulmonar , Humanos , Radioisótopos de Gálio , Projetos Piloto , Hipertensão Pulmonar Primária Familiar , Tomografia por Emissão de Pósitrons , Fibroblastos , Fluordesoxiglucose F18RESUMO
BACKGROUND: Functional assessment of myocardial ischemia is critical for patients with intermediate coronary stenosis. As the diagnosis performance of absolute quantification of myocardial blood flow (MBF) and myocardial flow reserve (MFR) by single-photon emission tomography (SPECT) has been proven, its prognostic value in patients with intermediate coronary stenosis remains to be evaluated. METHODS: Patients with one or more target lesions of ≥ 50% to ≤ 80% diameter stenoses on invasive coronary angiography were prospectively included in this study. All patients were scheduled for clinically indicated SPECT myocardial perfusion imaging (MPI) within 3 months and agreed to provide informed consent to participate in quantitative SPECT acquisitions to obtain MBF and MFR values. The primary endpoint was defined as a composite of the major adverse cardiac events (MACE): Cardiac death, myocardial infarction, late revascularization and heart failure or unstable angina-related rehospitalization. RESULTS: One hundred and nineteen patients (mean age 57 ± 8 years, 62.2% men) were included in the analysis. The average lumen stenosis of patients was 67.0 ± 10.4%. Over a median follow-up duration of 1408 days (interquartile range 1297-1666 days), 18 patients (15.1%) had MACE. Patients with impaired MFR (MFR < 2) had a significantly higher incidence of events than those with preserved MFR (MFR ≥ 2) in Kaplan-Meier survival analysis (Log-rank = 8.105, P = 0.004), while no significant difference was found between patients with normal relative perfusion and those with relative perfusion abnormalities (log-rank = 0.098, P > 0.05). In a multivariate Cox hazards analysis, the SPECT-derived MFR remained an independent predictor of MACE (HR 0.352, 95% CI 0.145-0.854, P = 0.021). CONCLUSIONS: In a cohort of patients with angiographic intermediate coronary lesions, SPECT-derived MFR was an independent predictor of prognosis.
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Doença da Artéria Coronariana , Estenose Coronária , Reserva Fracionada de Fluxo Miocárdico , Isquemia Miocárdica , Imagem de Perfusão do Miocárdio , Masculino , Humanos , Pessoa de Meia-Idade , Idoso , Feminino , Prognóstico , Tomografia Computadorizada de Emissão de Fóton Único/métodos , Estenose Coronária/diagnóstico por imagem , Angiografia Coronária/métodos , Imagem de Perfusão do Miocárdio/métodosRESUMO
The first examples of halogen bonding (XB) heteroditopic homo[2]catenanes were prepared by discrete Na+ template-directed assembly of oligo(ethylene glycol) units derived from XB donor-containing macrocycles and acyclic bis-azide precursors, followed by a CuI -mediated azide-alkyne cycloaddition macrocyclisation reaction. Extensive 1 Hâ NMR spectroscopic studies show the [2]catenane hosts exhibit positive cooperative ion-pair recognition behaviour, wherein XB-mediated halide recognition is enhanced by alkali metal cation pre-complexation. Notably, subtle changes in the catenanes' oligo(ethylene glycol) chain length dramatically alters their ion-binding affinity, stoichiometry, complexation mode, and conformational dynamics. Solution-phase and single-crystal X-ray diffraction studies provide evidence for competing host-separated and direct-contact ion-pair binding modes. We further demonstrate the [2]catenanes are capable of extracting solid alkali-metal halide salts into organic media.
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Chalcogen bonding (ChB) is rapidly rising to prominence in supramolecular chemistry as a powerful sigma (σ)-hole-based noncovalent interaction, especially for applications in the field of molecular recognition. Recent studies have demonstrated ChB donor strength and potency to be remarkably sensitive to local electronic environments, including redox-switchable on/off anion binding and sensing capability. Influencing the unique electronic and geometric environment sensitivity of ChB interactions through simultaneous cobound metal cation recognition, herein, we present the first potassium chloride-selective heteroditopic ion-pair receptor. The direct conjugation of benzo-15-crown-5 ether (B15C5) appendages to Te centers in a bis-tellurotriazole framework facilitates alkali metal halide (MX) ion-pair binding through the formation of a cofacial intramolecular bis-B15C5 M+ (M+ = K+, Rb+, Cs+) sandwich complex and bidentate ChB···X- formation. Extensive quantitative 1H NMR ion-pair affinity titration experiments, solid-liquid and liquid-liquid extraction, and U-tube transport studies all demonstrate unprecedented KCl selectivity over all other group 1 metal chlorides. It is demonstrated that the origin of the receptor's ion-pair binding cooperativity and KCl selectivity arises from an electronic polarization of the ChB donors induced by the cobound alkali metal cation. Importantly, the magnitude of this switch on Te-centered electrophilicity, and therefore anion-binding affinity, is shown to correlate with the inherent Lewis acidity of the alkali metal cation. Extensive computational DFT investigations corroborated the experimental alkali metal cation-anion ion-pair binding observations for halides and oxoanions.
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Calcogênios , Metais Alcalinos , Ânions/química , Cátions/química , Cloretos , Cloreto de PotássioRESUMO
A family of novel halogen bonding (XB) and hydrogen bonding (HB) heteroditopic [2]rotaxane host systems constructed by active metal template (AMT) methodology, were studied for their ability to cooperatively recognise lithium halide (LiX) ion-pairs. 1 Hâ NMR ion-pair titration experiments in CD3 CN:CDCl3 solvent mixtures revealed a notable "switch-on" of halide anion binding in the presence of a co-bound lithium cation, with rotaxane hosts demonstrating selectivity for LiBr over LiI. The strength of halide binding was shown to greatly increase with increasing number of halogen bond donors integrated into the interlocked cavity, where an all-XB rotaxane was found to be the most potent host for LiBr. DFT calculations corroborated these findings, determining the mode of LiX ion-pair binding. Notably, ion-pair binding was not observed with the corresponding XB/HB macrocycles alone, highlighting the cooperative, heteroditopic, rotaxane axle-macrocycle component mechanical bond effect as an efficient strategy for ion-pair recognition in general.
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Exceptionally strong halogen bonding (XB) donor-chloride interactions are exploited for the chloride anion template synthesis of neutral XB [2]rotaxane host systems which contain perfluoroaryl-functionalised axle components, including a remarkably potent novel 4,6-dinitro-1,3-bis-iodotriazole motif. Halide anion recognition properties in aqueous-organic media, determined via extensive 1 H NMR halide anion titration experiments, reveal the rotaxane host systems exhibit dramatically enhanced affinities for hydrophilic Cl- and Br- , but conversely diminished affinities for hydrophobic I- , relative to their non-interlocked axle counterparts. Crucially, this mechanical bond effect induces a binding selectivity which directly opposes Hofmeister bias. Free-energy analysis of this mechanical bond enhancement demonstrates anion recognition by neutral XB interlocked host systems as a rare and general strategy to engineer anti-Hofmeister bias anion selectivity in synthetic receptor design.
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To get carbon electrode with both excellent gravimetric and volumetric capacitances at high mass loadings is critical to supercapacitors. Herein, cracked defective graphene nanospheres (GNS) well meet above requirements. The morphology and structure of the GNS are controlled by polystyrene sphere template/glucose ratio, microwave heating time, and Fe content. The typical GNS with specific surface area of 2794 m2 g-1 , pore volume of 1.48 cm3 g-1 , and packing density of 0.74 g cm-3 performs high gravimetric and volumetric capacitances of 529 F g-1 and 392 F cm-3 at 1A g-1 with a capacitance retention of 62.5% at 100 A g-1 in a three-electrode system in 6 mol L-1 KOH aqueous electrolyte. In a two-electrode system, the GNS possesses energy density of 18.6 Wh kg-1 (13.8 Wh L-1 ) at the power density of 504 W kg-1 , which is higher than all reported pure carbon materials in gravimetric energy density and higher than all reported heteroatom-doped carbon materials in volumetric energy density, in aqueous solution, as far as it is known. A structural feature of carbon materials that possess both high energy density and high power density is pointed out here.
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Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. 1 H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P+. redox couple.
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Porfirinas , Rotaxanos , Ânions , Compostos de Boro , Halogênios , Ligação de HidrogênioRESUMO
A series of tetraphenylethene (TPE) derivatives functionalized with highly potent electron-deficient perfluoroaryl iodo-triazole halogen bond (XB) donors for anion recognition are reported. 1 Hâ NMR titration experiments, fluorescence spectroscopy, dynamic light scattering measurements, TEM imaging and X-ray crystal structure analysis reveal that the tetra-substituted halogen bonding receptor forms luminescent nanoscale aggregates, the formation of which is driven by XB-mediated anion coordination. This anion-coordination-induced aggregation effect serves as a powerful sensory mechanism, capable of luminescence chloride sensing at parts per billion concentration. Furthermore, the doubly substituted geometric isomers act as unprecedented photoswitchable XB donor anion receptors, where the composition of the photostationary state can be modulated by the presence of a coordinating halide anion.
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Background Accurate methods for identifying obstructions in both large and small vessels are crucial for diagnosis and treatment of chronic thromboembolic pulmonary hypertension (CTEPH). Purpose To compare the performance of ventilation-perfusion (V/Q) scanning, V/Q SPECT, and CT pulmonary angiography (PA) in CTEPH by using digital subtraction PA as the reference standard. Materials and Methods This prospective study was conducted from January 2016 to January 2018. A total of 229 participants suspected of having CTEPH were evaluated with V/Q SPECT, V/Q planar scintigraphy, CT PA, and digital subtraction PA. Participants underwent all four procedures within 1 week. Differences in the diagnostic performance of V/Q SPECT, V/Q planar scintigraphy, and CT PA were evaluated with areas under the curve receiver operator curve, the McNemar test, and generalized estimating equations analysis. Results A total of 150 participants (mean age, 42 years ± 15 [standard deviation]; 99 women) were enrolled. Digital subtraction PA assessments confirmed CTEPH in 51 participants and indicated that 602 of 1020 lung segments (20 segments per participant) were obstructed. The three imaging methods showed high sensitivity (V/Q SPECT, 98%; V/Q planar scintigraphy, 98%; CT PA, 94%) and specificity (V/Q SPECT, 89%; V/Q planar scintigraphy, 91%; CT PA, 96%) (all P > .05). However, both V/Q scanning techniques were more sensitive (V/Q SPECT: 85%, P < .001 vs CT PA: 67%; V/Q planar scintigraphy: 83%, P < .001 vs CT PA: 67%), and less specific (V/Q planar scintigraphy: 51%, P = .03 vs CT PA: 60%; V/Q SPECT: 42%, P < .01 vs CT PA: 60%) than was CT PA for segmental analysis. Areas under the curve for CT PA, V/Q planar scintigraphy, and V/Q SPECT were 0.95, 0.95, and 0.94, respectively (all P > .05), for individual analysis, and 0.64, 0.67, and 0.64, respectively, by segment (V/Q planar scintigraphy vs V/Q SPECT, P = .02; V/Q planar scintigraphy vs CT PA, P = .08; V/Q SPECT vs CT PA, P = .94). Conclusion Ventilation-perfusion scanning was more sensitive and less specific than was CT pulmonary angiography for detecting vascular obstructions at the segmental pulmonary arterial level. © RSNA, 2020 See also the editorial by Swift and Rajaram in this issue.
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Angiografia por Tomografia Computadorizada/métodos , Hipertensão Pulmonar/diagnóstico por imagem , Embolia Pulmonar/diagnóstico por imagem , Tomografia Computadorizada de Emissão de Fóton Único/métodos , Adulto , Idoso , Doença Crônica , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Estudos ProspectivosRESUMO
Several H-H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2 . Understanding HER processes, especially controllable switching between homolytic and heterolytic H-H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.
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AIM: The aim of this study was to compare CZT-SPECT (CZT SPECT) to conventional SPECT (C-SPECT) in the assessment of left ventricular myocardial scar, contractile function, and mechanical synchrony in patients with heart failure (HF). METHODS: Fifty-nine patients with HF who were referred for myocardial perfusion/metabolism imaging were enrolled. All patients underwent resting 99mTc-MIBI gated myocardial perfusion imaging using a CZT SPECT camera and a C-SPECT camera, respectively, and 18F-FDG PET myocardial metabolism imaging within three days. Summed rest score (SRS) and total perfusion defect (TPD) (as indices of perfusion abnormality), left ventricular (LV), end diastolic volume (EDV), end systolic volume (ESV), and ejection fraction (EF) (as indices of LV systolic function), and histogram band width (BW) and standard deviation (SD) (as indices of mechanical synchrony) were analyzed by automated software while the perfusion/metabolism patterns were analyzed visually. RESULTS: There was a good correlation between CZT SPECT and C-SPECT for SRS and TPD. CZT SPECT tended to underestimate SRS and TPD compared to C-SPECT. CZT-SPECT and C-SPECT showed excellent agreement in assessing the perfusion/metabolism pattern though a small proportion of normal segments (6.6%) identified by CZT/PET exhibited mismatch pattern on C-SPECT/PET. CZT SPECT also showed excellent correlation with C-SPECT in measuring EDV, ESV, and EF. Finally, BW and SD measured by CZT SPECT correlated well with C-SPECT but CZT SPECT tended to overestimate BW and SD compared to C-SPECT. CONCLUSION: CZT SPECT provided comparable data to C-SPECT for measuring LV scar, function and synchrony at a considerable reduction in imaging time. CZT SPECT holds a promise for comprehensive evaluation of myocardial performance in patients with HF.
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Cádmio , Cicatriz/diagnóstico por imagem , Insuficiência Cardíaca/diagnóstico por imagem , Ventrículos do Coração/diagnóstico por imagem , Telúrio , Tomografia Computadorizada de Emissão de Fóton Único/instrumentação , Tomografia Computadorizada de Emissão de Fóton Único/métodos , Zinco , Adulto , Idoso , Automação , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Isquemia Miocárdica/diagnóstico por imagem , Isquemia Miocárdica/patologia , Imagem de Perfusão do Miocárdio , Miocárdio , Semicondutores , Software , Volume Sistólico , Tecnécio Tc 99m Sestamibi , Função Ventricular EsquerdaRESUMO
Water splitting is promising to realize a hydrogen-based society. The practical use of molecular water-splitting catalysts relies on their integration onto electrode materials. We describe herein the immobilization of cobalt corroles on carbon nanotubes (CNTs) by four strategies and compare the performance of the resulting hybrids for H2 and O2 evolution. Co corroles can be covalently attached to CNTs with short conjugated linkers (the hybrid is denoted as H1) or with long alkane chains (H2), or can be grafted to CNTs via strong π-π interactions (H3) or via simple adsorption (H4). An activity trend H1â«H3>H2≈H4 is obtained for H2 and O2 evolution, showing the critical role of electron transfer ability on electrocatalysis. Notably, H1 is the first Janus catalyst for both H2 and O2 evolution reactions in pHâ 0-14 aqueous solutions. Therefore, this work is significant to show potential uses of electrode materials with well-designed molecular catalysts in electrocatalysis.
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Water-soluble copper(II) complexes of the dianionic tridentate pincer ligand N,N'-2,6-dimethylphenyl-2,6-pyridinedicarboxamidate (L) are catalysts for water oxidation. In [L-CuII-DMF] (1, DMF = dimethylformamide) and [L-CuII-OAc]- (2, OAc = acetate), ligand L binds CuII through three N atoms, which define an equatorial plane. The fourth coordination site of the equatorial plane is occupied by DMF in 1 and by OAc- in 2. These two complexes can electrocatalyze water oxidation to evolve O2 in 0.1 M pH 10 carbonate buffer. Spectroscopic, titration, and crystallographic studies show that both 1 and 2 undergo ligand exchange when they are dissolved in carbonate buffer to give [L-CuII-CO3H]- (3). Complex 3 has a similar structure as those of 1 and 2 except for having a carbonate group at the fourth equatorial position. A catalytic cycle for water oxidation by 3 is proposed based on experimental and theoretical results. The two-electron oxidized form of 3 is the catalytically active species for water oxidation. Importantly, for these two oxidation events, the calculated potential values of Ep,a = 1.01 and 1.59 V vs normal hydrogen electrode (NHE) agree well with the experimental values of Ep,a = 0.93 and 1.51 V vs NHE in pH 10 carbonate buffer. The potential difference between the two oxidation events is 0.58 V for both experimental and calculated results. With computational evidence, this Cu-bound carbonate group may act as a proton shuttle to remove protons for water activation, a key role resembling intramolecular bases as reported previously.
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A series of cobalt complexes of 5,10,15-tris(pentafluorophenyl)-corrole [Co(tpfc)] (1) with various axial ligands were synthesized and examined as single-site catalysts for water oxidation. The used axial ligands include 4-cyanopyridine (py-CN), pyridine (py), 4-(dimethylamino)pyridine (py-NMe2), 4-methoxypyridine (py-OMe), 1-methylimidazole (im-Me), and thiophenolate (thi). Complexes 1-py and 1-py-OMe were structurally characterized. The Co ion in both structures has an almost identical distorted octahedral coordination environment with the four N atoms of tpfc defining the equatorial plane and the two molecules of pyridine (for 1-py) or 4-methoxypyridine (for 1-py-OMe) occupying the axial positions. Electrochemical studies of these Co corroles in acetonitrile showed that they all display two oxidation events and the oxidation waves shift to the cathodic direction with electron-donating axial ligands, a trend that is consistent with increased electron densities on Co ions. All these Co corroles were found to be active for electrocatalytic water oxidation: by using catalyst-coated fluorine-doped tin oxide (FTO) working electrodes, cyclic voltammograms displayed pronounced catalytic waves for water oxidation in 0.1 M pH 7.0 phosphate buffer solutions. The onset overpotentials are in the range of 510 to 580 mV, depending on the electron-donating ability of the trans axial ligands. These results demonstrate that the catalytic activities of Co corroles for water oxidation are considerably affected by the trans axial ligands on Co centers and provide valuable insights into the design of new catalysts for water oxidation.