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1.
Proc Natl Acad Sci U S A ; 120(52): e2310916120, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38117856

RESUMO

The kinetics and pathway of most catalyzed reactions depend on the existence of interface, which makes the precise construction of highly active single-atom sites at the reaction interface a desirable goal. Herein, we propose a thermal printing strategy that not only arranges metal atoms at the silica and carbon layer interface but also stabilizes them by strong coordination. Just like the typesetting of Chinese characters on paper, this method relies on the controlled migration of movable nanoparticles between two contact substrates and the simultaneous emission of atoms from the nanoparticle surface at high temperatures. Observed by in situ transmission electron microscopy, a single Fe3O4 nanoparticle migrates from the core of a SiO2 sphere to the surface like a droplet at high temperatures, moves along the interface of SiO2 and the coated carbon layer, and releases metal atoms until it disappears completely. These detached atoms are then in situ trapped by nitrogen and sulfur defects in the carbon layer to generate Fe single-atom sites, exhibiting excellent activity for oxygen reduction reaction. Also, sites' densities can be regulated by controlling the size of Fe3O4 nanoparticle between the two surfaces. More importantly, this strategy is applicable to synthesize Mn, Co, Pt, Pd, Au single-atom sites, which provide a general route to arrange single-atom sites at the interface of different supports for various applications.

2.
J Am Chem Soc ; 146(7): 4883-4891, 2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38326284

RESUMO

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

3.
J Am Chem Soc ; 145(24): 13462-13468, 2023 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-37293805

RESUMO

Arranging atoms in an orderly manner at the atomic scale to create stable polyatomic structures is a very challenging task. In this study, we have developed three-dimensional confinement areas on the two-dimensional surface by creating regional defects. These areas are composed of vertically stacked graphene layers, where Ni and Fe atoms are anchored concentrically to form axial dual atomic sites in high yield. These sites can be used to produce tunable syngas through the electroreduction of CO2. Theoretical calculations indicate that the Ni sites vertically regulate the charge distribution of the adjacent Fe sites in the layer below, resulting in a lower d-band center. This, in turn, weakens the adsorption of the *CO intermediate and inhibits the production of H2 at the Fe site. Our research presents a novel approach for concentrated creation of dual atomic sites by building a confinement-selective surface.

4.
Small ; 19(45): e2302328, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37431211

RESUMO

The design of an efficient catalytic system with low Pt loading and excellent stability for the acidic oxygen reduction reaction is still a challenge for the extensive application of proton-exchange membrane fuel cells. Here, a gas-phase ordered alloying strategy is proposed to construct an effective synergistic catalytic system that blends PtM intermetallic compounds (PtM IMC, M = Fe, Cu, and Ni) and dense isolated transition metal sites (M-N4 ) on nitrogen-doped carbon (NC). This strategy enables Pt nanoparticles and defects on the NC support to timely trap flowing metal salt without partial aggregation, which is attributed to the good diffusivity of gaseous transition metal salts with low boiling points. In particular, the resulting Pt1 Fe1 IMC cooperating with Fe-N4 sites achieves cooperative oxygen reduction with a half-wave potential up to 0.94 V and leads to a high mass activity of 0.51 A  mgPt -1 and only 23.5% decay after 30 k cycles, both of which exceed DOE 2025 targets. This strategy provides a method for reducing Pt loading in fuel cells by integrating Pt-based intermetallics and single transition metal sites to produce an efficient synergistic catalytic system.

5.
Langmuir ; 39(34): 12260-12269, 2023 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-37582181

RESUMO

Adsorbate transport during the electrochemical process mostly follows the electric-field direction or the high-to-low direction along the concentration gradient and thus often limits the reactant concentration at the adsorption site and requires specific mechanical or chemical bonds of adsorbates to trigger local excess aggregation for advanced framework structure assembly. Herein, we have discovered an active pumping channel during electrochemical adsorption of a manganese colloid, which follows a low-to-high direction inverse concentration gradient. It triggers surface excess micelle aggregation with even over 16-folds higher concentration than that in bulk owing to hydrogen-bonding difference of the micelle surface between in bulk and at the water surface. Micelles in the channel exhibit unique polymerization behaviors by directly polymerizing monomer micelles to form highly catalytic MnO2 of dendritic frameworks, which can serve as a scalable thin-layer aqueous-phase reactor. It increases the understanding of the interface-dependent dynamic nature of micelle or more adsorbates and inspires transformative synthesizing approaches for advanced oxide materials.

6.
Eur Radiol ; 33(7): 5118-5130, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36725719

RESUMO

OBJECTIVES: To develop an artificial intelligence (AI) model for prostate segmentation and prostate cancer (PCa) detection, and explore the added value of AI-based computer-aided diagnosis (CAD) compared to conventional PI-RADS assessment. METHODS: A retrospective study was performed on multi-centers and included patients who underwent prostate biopsies and multiparametric MRI. A convolutional-neural-network-based AI model was trained and validated; the reliability of different CAD methods (concurrent read and AI-first read) were tested in an internal/external cohort. The diagnostic performance, consistency and efficiency of radiologists and AI-based CAD were compared. RESULTS: The training/validation/internal test sets included 650 (400/100/150) cases from one center; the external test included 100 cases (25/25/50) from three centers. For diagnosis accuracy, AI-based CAD methods showed no significant differences and were equivalent to the radiologists in the internal test (127/150 vs. 130/150 vs. 125/150 for reader 1; 127/150 vs.132/150 vs. 131/150 for reader 2; all p > 0.05), whereas in the external test, concurrent-read methods were superior/equal to AI-first read (87/100 vs. 71/100, p < 0.001, for reader 2; 79/100 vs. 69/100, p = 0.076, for reader 1) and better than/equal to radiologists (79/100 vs. 72/100, p = 0.039, for reader 1; 87/100 vs. 86/100, p = 1.000, for reader 2). Moreover, AI-first read/concurrent read improved consistency in both internal test (κ = 1.000, 0.830) and external test (κ = 0.958, 0.713) compared to radiologists (κ = 0.747, 0.600); AI-first read method (8.54 s/7.66 s) was faster than readers (92.72 s/89.54 s) and concurrent-read method (29.15 s/28.92 s), respectively. CONCLUSION: AI-based CAD could improve the consistency and efficiency for accurate diagnosis; the concurrent-read method could enhance the diagnostic capabilities of an inexperienced radiologist in unfamiliar situations. KEY POINTS: • For prostate cancer segmentation, the performance of multi-small Vnet displays optimal compared to small Vnet and Vnet (DSCmsvnet vs. DSCsvnet, p = 0.021; DSCmsvnet vs. DSCvnet, p < 0.001). • For prostate gland segmentation, the mean/median DSCs for fine and coarse segmentation were 0.91/0.91 and 0.88/0.89, respectively. Fine segmentation displays superior performance compared to coarse (DSCcoarse vs. DSCfine, p < 0.001). • For PCa diagnosis, AI-based CAD methods improve consistency in internal (κ = 1.000; 0.830) and external (κ = 0.958; 0.713) tests compared to radiologists (κ = 0.747; 0.600); the AI-first read (8.54 s/7.66 s) was faster than the readers (92.72 s/89.54 s) and the concurrent-read method (29.15 s/28.92 s).


Assuntos
Imageamento por Ressonância Magnética , Neoplasias da Próstata , Masculino , Humanos , Imageamento por Ressonância Magnética/métodos , Próstata/diagnóstico por imagem , Próstata/patologia , Neoplasias da Próstata/diagnóstico por imagem , Neoplasias da Próstata/patologia , Inteligência Artificial , Estudos Retrospectivos , Reprodutibilidade dos Testes , Computadores
7.
Inorg Chem ; 62(46): 19123-19134, 2023 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-37945002

RESUMO

Electrochemical hydrogeneration (ECH) of biomass-derived platform molecules, which avoids the disadvantages in utilizing fossil fuel and gaseous hydrogen, is a promising route toward value-added chemicals production. Herein, we reported a CoO/Co heterostructure-supported Pt single atoms electrocatalyst (Pt1-CoO/Co) that exhibited an outstanding performance with a high conversion (>99%), a high Faradaic efficiency (87.6%), and robust stability (24 recyclability) at -20 mA/cm2 for electrochemical phenol hydrogenation to high-valued KA oil (a mixture of cyclohexanol and cyclohexanone). Experimental results and the density functional theory calculations demonstrated that Pt1-CoO/Co presented strong adsorption of phenol and hydrogen on the catalyst surface simultaneously, which was conducive to the transfer of the adsorbed hydrogen generated on the single atom Pt sites to activated phenol, and then, ECH of phenol with high performance was achieved instead of the direct hydrogen evolution reaction. This work described that the multicomponent synergistic single atom catalysts could effectively accelerate the ECH of phenol, which could help the achievement of large-scale biomass upgrading.

8.
Angew Chem Int Ed Engl ; 62(12): e202300879, 2023 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-36721306

RESUMO

Charge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic-tuned RuBi SAA/Bi@OG nanostructure that features RuBi single-atom alloy nanoparticle supported by Bi-O single-site-doped graphene was successfully developed by one-step pyrolysis method. The alloyed Bi single atom and adjacent Bi-O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg-1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen-adsorption free energy in HER process. This double atomic-tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts.

9.
J Am Chem Soc ; 144(35): 15999-16005, 2022 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-35998643

RESUMO

The orderly assembly of single atoms into highly periodic aggregates at the nanoscale is an intriguing but challenging process of high-precision atomic manufacturing. Here, we discover that an in-plane film surface shrinkage can induce molecular self-assembly to arrange single atoms with unconventional distribution, contributing them to periodic one-dimensional segregation on carbon stripes (one-dimensional single-atom arrays (SAA)). This originates from the fact that metal phthalocyanine (MPc) molecules gradually aggregate and melt to form a film under a thermal drive and the help of sodium chloride templates, accompanied by surface shrinkage, self-assembly, and deep carbonization. At the nanoscale, these periodic parallel arrays are formed due to MPc molecular interactions by π-π stacking. At the atomic scale, the single atoms are stabilized by the vertical phthalocyanine-derived multilayer graphene. This can significantly modify the electronic structure of the single-atom sites on the outermost graphene (e.g., Fe-based SAA), thus optimizing the adsorption energy of oxygen intermediates and resulting in a superior oxygen reduction reaction (ORR) performance concerning disordered single atoms. Our findings provide a general route for orderly single-atom manufacturing (e.g., Fe, Co, and Cu) and an understanding of the relationship between orderly allocation and catalytic performance.

10.
Small ; 18(44): e2204015, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36123142

RESUMO

The catalytic activity and selectivity of single-atom sites catalysts is strongly dependent on the supports structure and central metal coordination environment. However, the further optimization of electronic configuration to improve the catalytic performance is usually hampered by the strong coordination effect between the support and metal atoms. Herein, it is discovered that enzyme-mimicking catalytic performance can be enhanced at the fixed coordination single-atom Fe sites by regulating the Fe spin states. The X-ray absorption fine structure, 57 Fe Mössbauer spectrum, and temperature-dependent magnetization measurements reveal that the spin states of Fe in single FeN4  sites can be well manipulated via changing the pyrolysis temperature. The intermediate-spin Fe sites catalyst (t2g 4 eg 1) demonstrates a much higher peroxidase-mimicking activity in comparison with high-spin structure (t2g 3 eg 2). More importantly, the based enzymes system realizes sensitive detection of H2 O2  and glucose by colorimetric sensors with high catalytic activity and selectivity. Furthermore, theoretical calculations unveil that the intermediate-spin FeN4  promotes the OH* desorption process, thus greatly reducing the reaction energy barrier. These findings provide a route to design highly active enzyme-mimicking catalysts and an engineering approach for regulating spin states of metal sites to enhance their catalytic performance.


Assuntos
Ferro , Peroxidase , Ferro/química , Oxirredução , Catálise , Oxirredutases , Peroxidases
11.
Neurol Sci ; 43(1): 467-476, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34052937

RESUMO

OBJECTIVE: Bipolar disorder (BD) may be associated with an increased risk of stroke, but to date, the results of the studies are still controversial. This study aimed to assess the association of BD with stroke incidence and mortality by a meta-analysis. METHOD: PubMed, EMBASE, the Cochrane library databases, and Web of Science databases were searched from inception to July 2020. We regarded stroke as a composite endpoint. The pooled hazard ratio (HRs) of 95% confidence interval (Cls) was calculated. Subgroup and sensitivity analyses were performed to assess the potential sources of heterogeneity of the pooled estimation. RESULTS: A total of 7 studies involving a total of 13,305,007 participants were included in this meta-analysis. Pooled analysis showed participants with BD experienced a significantly increased risk of both stroke incidence (combined HR, 1.43; 95% CI, 1.24-1.66; p = 0.000) and stroke mortality (combined HR, 1.54; 95% CI, 1.09-2.18; p = 0.013) compared to participants without BD. In addition, the pooled estimate of multivariate HRs of stroke incidence and mortality were 1.35 (95% CI: 1.26-1.45); 2.30 ( 95% CI: 1.37-3.85) among men and 1.43 (95% CI:1.27-1.60); 2.08 (95% CI:1.60-2.71) among women respectively. CONCLUSIONS: This meta-analysis suggests that BD may modestly increase the risk of both stroke incidence and mortality. Extensive clinical observational studies should be conducted in the future to explore whether BD is a potentially modifiable risk factor for stroke.


Assuntos
Transtorno Bipolar , Acidente Vascular Cerebral , Transtorno Bipolar/epidemiologia , Feminino , Humanos , Incidência , Masculino , Modelos de Riscos Proporcionais , Fatores de Risco , Acidente Vascular Cerebral/epidemiologia
12.
Appl Opt ; 61(27): 7958-7965, 2022 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-36255916

RESUMO

We present an adaptive optics (AO) system for a 1.94-µm laser source. Our system consists of a home-made Shack-Hartmann wavefront sensor and silver-coated bimorph deformable mirror operating in a closed-loop control scheme. The wavefront sensor used an uncooled vapor phase deposition PbSe focal-plane array for the actual light sensing. An effect of thermal afterimage was found to be reducing the centroid detection precision significantly. The effect was analyzed in detail and finally has been dealt with by updating the background calibration. System stability was increased by reduction of control modes. The system functionality and stability were demonstrated by improved focal spot quality. By replacing some of the used optics, the range of the demonstrated mid-IR AOS could be extended to cover the spectral range of 1-5 µm. To the best of our knowledge, it is the first AO system built specifically for mid-IR laser wavefront correction.

13.
J Ren Nutr ; 32(5): 595-604, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-34756787

RESUMO

OBJECTIVES: The present study aimed to explore the efficacy and safety of roxadustat in patients with renal anemia and erythropoietin (EPO) hyporesponsive who are receiving continuous ambulatory peritoneal dialysis (CAPD). METHODS: This is a single center, before and after treatment, self-controlled study; 55 CAPD patients with renal anemia and EPO hyporesponsiveness were enrolled. The main follow-up parameters included routine blood, liver and kidney function, electrolyte, blood lipid, high-sensitivity C-reactive protein, and iron tests. Serum samples were used to determine interleukin-6 and tumor necrosis factor-α levels via enzyme linked immunosorbent assay. The Modified Quantitative Subjective Global Assessment Score and Malnutrition-Inflammation Score before and after treatment, and adverse events during treatment were recorded. The follow-up observation time was 12 weeks. Preliminary data 12-24 weeks before the enrollment as well as post-follow-up data at 36 weeks were also collected. RESULTS: Fifty patients completed the 12-week follow-up. The hemoglobin levels were 8.0 ± 1.2 g/dL at baseline and 11.2 ± 2.0 g/dL after 12 weeks of roxadustat treatment. The hemoglobin increases at all measured time points and was statistically significant compared with the baseline value (P < .05). The overall hemoglobin response rate (hemoglobin increase ≥ 1.0 g/dL) was 80%, and 50% of the patients reached the hemoglobin target (hemoglobin ≥ 11.0 g/dL) at 12 weeks. Transferrin was higher at 12 weeks (2.2 ± 0.5 g/L) than at baseline (1.7 ± 0.5 g/L) (P < .05), while serum ferritin levels slightly decreased compared with the baseline value (P > .05). The median high-sensitivity C-reactive protein level and other inflammation-related indicators, such as white blood cell counts, neutrophil-to-lymphocyte ratio, platelet-to-lymphocyte ratio, interleukin-6, and tumor necrosis factor-α, were not significantly different from their baseline values. Nutrition-related biochemical indices such as albumin, creatinine, and blood lipids were also not significantly changed. The Modified Quantitative Subjective Global Assessment Score and Malnutrition-Inflammation Score were slightly lower at 12 weeks than at baseline. No serious adverse events were observed during the follow-up period. Post-follow-up data revealed a maintained hemoglobin level in patients who remained on roxadustat treatment while those switched back to EPO treatment after 12 weeks resulted in a decreased hemoglobin at 36 weeks. CONCLUSIONS: In patients with EPO hyporesponsiveness on CAPD, roxadustat can efficiently and safely improve anemia and nutritional status without promoting inflammation.


Assuntos
Anemia , Eritropoetina , Desnutrição , Diálise Peritoneal , Anemia/tratamento farmacológico , Anemia/etiologia , Proteína C-Reativa/metabolismo , Eritropoetina/uso terapêutico , Glicina/análogos & derivados , Hemoglobinas/metabolismo , Humanos , Inflamação , Interleucina-6 , Isoquinolinas , Projetos Piloto , Estudos Prospectivos , Diálise Renal , Fator de Necrose Tumoral alfa
14.
Angew Chem Int Ed Engl ; 61(47): e202212329, 2022 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-36098059

RESUMO

Single atom catalysts (SACs) have been widely studied in the field of CO2 electroreduction, but industrial-level current density and near-unity product selectivity are still difficult to achieve. Herein, a diatomic site catalysts (DASCs) consisting of Co-Cu hetero-diatomic pairs is synthesized. The CoCu DASC exhibits excellent selectivity with the maximum CO Faradaic efficiency of 99.1 %. The CO selectivity can maintain above 95 % over a wide current density range from 100 mA cm-2 to 500 mA cm-2 . The maximum CO partial current density can reach to 483 mA cm-2 in flow cell, far exceed industrial-level current density requirements (>200 mA cm-2 ). Theoretical calculation reveals that the synergistic catalysis of the Co-Cu bimetallic sites reduce the activation energy and promote the formation of intermediate *COOH. This work shows that the introduction of another metal atom into SACs can significantly affect the electronic structure and then enhance the catalytic activity of SACs.

15.
Neurol Sci ; 42(11): 4521-4529, 2021 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-33606128

RESUMO

BACKGROUND: Many studies have described the relationship between kidney stones and stroke, but the results are controversial, so we conducted this meta-analysis to estimate the relationship between kidney stones and the risk of developing stroke. METHODS: Studies were marked with a comprehensive search of PubMed, EMBASE, Google, and ISI Web of Science databases through 25 March 2020. Hazard ratios (HRs) and 95% confidence intervals (CIs) were extracted, and a random-effects model or fix-effects model was used to compute the pooled combined risk estimate. Heterogeneity was reported as I2. We performed subgroup and sensitivity analysis to assess potential sources of heterogeneity. RESULTS: Eight studies of seven articles involving 3,526,808 participants were included in the meta-analysis. Overall, kidney stones were associated with a moderate risk of stroke incidence (HR, 1.24; 95% CI, 1.11-1.40; I2=79.6%; p=0.000). We conducted a sensitivity analysis by removing the studies that had a high risk of bias. Heterogeneity subsequently decreased significantly, while an increased risk of stroke in patient with kidney stones was again demonstrated (HR, 1.16; 95% CI, 1.11-1.23; I2=28.7%; p=0.000). Stratifying analysis showed that the results were more pronounced for ischemic stroke (HR, 1.14; 95% CI, 1.08-1.22; I2=15.6%; p=0.00) and the follow-up duration ≥10 years (HR, 1.18; 95% CI, 1.10-1.27; I2=31.6%; p=0.003). CONCLUSIONS: Our meta-analysis suggests that patients with kidney stones may have a modestly increased risk of developing stroke, especially in ischemic stroke. More large-scaled and clinical trials should be done to identify the relative impact of kidney stones on stroke outcomes in the future.


Assuntos
Cálculos Renais , Acidente Vascular Cerebral , Humanos , Incidência , Cálculos Renais/epidemiologia , Acidente Vascular Cerebral/epidemiologia
16.
Angew Chem Int Ed Engl ; 60(42): 22722-22728, 2021 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-34402159

RESUMO

Designing and modulating the local structure of metal sites is the key to gain the unique selectivity and high activity of single metal site catalysts. Herein, we report strain engineering of curved single atomic iron-nitrogen sites to boost electrocatalytic activity. First, a helical carbon structure with abundant high-curvature surface is realized by carbonization of helical polypyrrole that is templated from self-assembled chiral surfactants. The high-curvature surface introduces compressive strain on the supported Fe-N4 sites. Consequently, the curved Fe-N4 sites with 1.5 % compressed Fe-N bonds exhibit downshifted d-band center than the planar sites. Such a change can weaken the bonding strength between the oxygenated intermediates and metal sites, resulting a much smaller energy barrier for oxygen reduction. Catalytic tests further demonstrate that a kinetic current density of 7.922 mA cm-2 at 0.9 V vs. RHE is obtained in alkaline media for curved Fe-N4 sites, which is 31 times higher than that for planar ones. Our findings shed light on modulating the local three-dimensional structure of single metal sites and boosting the catalytic activity via strain engineering.

17.
J Am Chem Soc ; 142(29): 12643-12650, 2020 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-32584563

RESUMO

The controllable synthesis of stable single-metal site catalysts with an expected coordination environment for high catalytic activity and selectivity is still challenging. Here, we propose a cation-exchange strategy for precise production of an edge-rich sulfur (S) and nitrogen (N) dual-decorated single-metal (M) site catalysts (M = Cu, Pt, Pd, etc.) library. Our strategy relies on the anionic frameworks of sulfides and N-rich polymer shell to generate abundant S and N defects during high-temperature annealing, further facilitating the stabilization of exchanged metal species with atomic dispersion and excellent accessibility. This process was traced by in situ transmission electron microscopy, during which no metal aggregates were observed. Both experiments and theoretical results reveal the precisely obtained S, N dual-decorated Cu sites exhibit a high activity and low reaction energy barrier in catalytic hydroxylation of benzene at room temperature. These findings provide a route to controllably produce stable single-metal site catalysts and an engineering approach for regulating the central metal to improve catalytic performance.

18.
Small ; 16(31): e2002343, 2020 08.
Artigo em Inglês | MEDLINE | ID: mdl-32597016

RESUMO

Nanomaterials with enzyme-mimicking characteristics have engaged great awareness in various fields owing to their comparative low cost, high stability, and large-scale preparation. However, the wide application of nanozymes is seriously restricted by the relatively low catalytic activity and poor specificity, primarily because of the inhomogeneous catalytic sites and unclear catalytic mechanisms. Herein, a support-sacrificed strategy is demonstrated to prepare a single iron site nanozyme (Fe SSN) dispersed on the porous N-doped carbon. With well-defined coordination structure and high density of active sites, the Fe SSN performs prominent peroxidase-like activity by efficiently activating H2 O2 into hydroxyl radical (•OH) species. Furthermore, the Fe SSN is applied in colorimetric detection of glucose through a multienzyme biocatalytic cascade platform. Moreover, a low-cost integrated agarose-based hydrogel colorimetric biosensor is designed and successfully achieves the visualization evaluation and quantitative detection of glucose. This work expands the application of single-site catalysts in the fields of nanozyme-based biosensors and personal biomedical diagnosis.


Assuntos
Técnicas Biossensoriais , Nanoestruturas , Colorimetria , Glucose , Ferro
19.
J Org Chem ; 85(10): 6261-6270, 2020 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-32281374

RESUMO

A direct aerobic oxidative dehydrogenative coupling reaction of glycine esters with ß-naphthols has been achieved via the synergistic combination of photoredox catalysis and Lewis acid catalysis. A wide range of glycine esters and ß-naphthols are suitable substrates for this reaction. A variety of 1,3-benzoxazines were obtained in good yields with excellent diastereoselectivities under mild reaction conditions. Moreover, this protocol could be performed on a gram-scale without considerable loss in activity.

20.
J Appl Clin Med Phys ; 21(8): 256-262, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32510768

RESUMO

This retrospective study was to compare the image quality of right coronary artery (RCA) and effective radiation dose on prospective ECG-gated method between 320 row computed tomography (CT) and 2nd generation (128-slice) dual source CT. A total of 215 candidates underwent CT coronary angiography using prospective ECG-gated method, 120 patients enrolled in 320 row CT group, and 95 patients in dual source CT group. We divided RCA image quality scores as 1/2/3/4, which means excellent/good/adequate/not assessable and heart rates were considered, as well as the radiation dose. There is no statistically significant difference of RCA image quality of Score 1/2 between 320 row CT and 2nd generation dual source CT, but lower heart rate (<70/min) improved RCA image quality. Meanwhile, the 2nd generation dual source CT scan have significant lower radiation dose. For patients with high level heart rate variation, both prospective ECG-gated method of 320 row CT scan (Toshiba) and 2nd generation dual source CT scan (Siemens) basically provided good image quality on RCA. There is an advantage of effective radiation dose reduction in prospective ECG-gated method using the 2nd generation dual source CT scan. After the iodine contrast agent was injected into elbow vein, the threshold triggering method was used to carry out prospective gated scanning, and the acquired fault image was reconstructed by the standard post-processing software of each manufacturer. The radiation dose value is obtained through the dose report automatically generated after each scan.


Assuntos
Vasos Coronários , Eletrocardiografia , Técnicas de Imagem de Sincronização Cardíaca , Angiografia Coronária , Vasos Coronários/diagnóstico por imagem , Humanos , Estudos Prospectivos , Doses de Radiação , Estudos Retrospectivos , Tomografia Computadorizada por Raios X
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