Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 63
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Artigo em Inglês | MEDLINE | ID: mdl-32227541

RESUMO

The hydroxide-exchange membrane fuel cell (HEMFC) is a promising energy conversion device. However, the development of HEMFC is hampered by the lack of platinum-group-metal-free (PGM-free) electrocatalysts for the hydrogen oxidation reaction (HOR). Now, a Ni catalyst is reported that exhibits the highest mass activity in HOR for a PGM-free catalyst as well as excellent activity in the hydrogen evolution reaction (HER). This catalyst, Ni-H2 -2 %, was optimized through pyrolysis of a Ni-containing metal-organic framework precursor under a mixed N2 /H2 atmosphere, which yielded carbon-supported Ni nanoparticles with different levels of strains. The Ni-H2 -2 % catalyst has an optimal level of strain, which leads to an optimal hydrogen binding energy and a high number of active sites.

2.
Artigo em Inglês | MEDLINE | ID: mdl-32337762

RESUMO

Electrochemical conversion of CO2 to ethane is seldom observed because of the generally higher selectivity towards methane, ethylene, and ethanol. Consequently, little experimental evidence for its reaction mechanism exists and thus remains largely unknown. Here, by combining electrochemistry with in-situ X-ray absorption fine structure and in-situ Raman techniques, we study iodide-derived copper (ID-Cu) and oxide-derived copper (OD-Cu) systems to obtain a deeper understanding of the CO2 to ethane mechanism. With trace iodine species on the surface and positively charged Cu species, production of ethane is significantly more favored on ID-Cu compared to OD-Cu, with higher selectivity and faster kinetics. For the first time, it is experimentally found that the formation of ethane follows the same pathway to ethylene and ethanol, and better stabilization of the late stage ethoxy intermediate can steer the reaction to ethane over ethanol.

3.
Pharmacol Rep ; 72(1): 208-213, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-32016842

RESUMO

BACKGROUND: αB-crystallin (CRYAB) is a small heat shock protein that is able to inhibit neuroinflammatory responses under various pathological conditions. Some studies have proven that neuroinflammatory mechanisms play important roles in bone cancer pain (BCP). However, whether CRYAB participates in the maintenance of BCP has not yet been examined. METHODS: Walker256 tumour cells were inoculated into the tibia to induce a rat model of BCP. Von Frey hairs were used to measure mechanical allodynia. Immunohistochemistry and western blotting were used to examine the expression level of CRYAB in the spinal dorsal horn. RESULTS: The gradual development of mechanical allodynia was induced by the injection of Walker256 cells into the tibia. The downregulation of spinal CRYAB expression was found in BCP rats. The intrathecal administration of CRYAB (from days 9 to 15 post-inoculation) dose-dependently alleviated mechanical allodynia in BCP rats. Additionally, there were concomitant increases in spinal CRYAB expression and decreases in TNF-α expression. CONCLUSIONS: Spinal CRYAB may participate in the maintenance of BCP in rats. The findings will help to identify new drugs for the management of BCP.

4.
ACS Appl Mater Interfaces ; 11(43): 40050-40061, 2019 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-31596062

RESUMO

In this study, we synthesized four acceptor-donor-acceptor type hole-transporting materials (HTMs) of SY1-SY4 for an HTMs/interfacial layer with carbazole as the core moiety and ester/amide as the acceptor unit. These HTMs contain 4-hexyloxyphenyl substituents on the carbazole N atom, with extended π-conjugation achieved through phenylene and thiophene units at the 3,6-positions of the carbazole. When using amide-based HTMs SY2 as a dopant-free HTM in a p-i-n perovskite solar cell (PSC), we achieved a power conversion efficiency (PCE) of 13.59% under AM 1.5G conditions (100 mW cm-2); this PCE was comparable with that obtained when using PEDOT:PSS as the HTM (12.33%). Amide-based SY2 and SY4 HTMs showed a larger perovskite grain than SY1 and SY3 because of the passivation of traps/defects at the grain boundaries and stronger interaction with the perovskite layer. In further investigation, we demonstrated highly efficient and stable PSCs when using the dopant-free p-i-n device structure indium tin oxide/NiOx/interfacial layer (SY-HTMs)/perovskite/PC61BM/BCP/Ag. The interfacial layer improved the PCEs and large grain size (micrometer scale) of the perovskite layer because of defect passivation and interface modification; the amide group exhibited a Lewis base adduct property coordinated to Ni and Pb ions in NiOx and perovskite, bifacial defect passivation and reduced the grain boundaries to improve the crystallinity of the perovskite. The amide-based SY2 exhibited the stronger interaction with the perovskite layer than that of ester-based SY1, which is related to the observations in X-ray absorption near edge structure (XANES). The best performance of the NiOx/SY2 device was characterized by a short-circuit current density (Jsc) of 21.76 mA cm-2, an open-circuit voltage (Voc) of 1.102 V, and a fill factor of 79.1%, corresponding to an overall PCE of 18.96%. The stability test of the PCE of the NiOx/SY2 PSC device PCE showed a decay of only 5.01% after 168 h; it retained 92.01% of its original PCE after 1000 h in Ar atmosphere. Time-resolved photoluminescence spectra of the perovskite films suggested that the hole extraction capabilities of the NiOx/SY-HTMs were better than that of the bare NiOx. The superior film morphologies of the NiOx/SY-HTMs were responsible for the performances of their devices being comparable with those of bare NiOx-based PSCs. The photophysical properties of the HTMs were analyzed through time-dependent density functional theory with the B3LYP functional.

5.
BMC Cardiovasc Disord ; 19(1): 188, 2019 08 05.
Artigo em Inglês | MEDLINE | ID: mdl-31382884

RESUMO

BACKGROUND: Coronary artery aneurysm (CAA) is a rare disease, and there are limited data on prescribing patterns for CAA. The aim of our study was to investigate prescribing patterns for CAA in Taiwan via the National Health Insurance Research Database (NHIRD). METHODS: We included all CAA patients in Taiwan from 2005 to 2011. Data from 1 year before and after the CAA diagnosis were used to analyze examinations, comorbidities and prescribing patterns. RESULTS: A total of 1397 patients diagnosed with CAA were enrolled in our study. Most pediatric patients with CAA were diagnosed with Kawasaki disease (95.7%). In pediatric CAA patients, the utilization rates of aspirin and gamma globulins were 82.9 and 53.6%, respectively, after CAA diagnosis. Among the antithrombotic agents, aspirin was used most commonly, followed by dipyridamole (16.9%), heparin (5.8%) and warfarin (4.6%). In adult CAA patients, common comorbidities included hypertension (63.4%), hyperlipidemia (39.6%), and diabetes mellitus (26.1%). Coronary atherosclerosis was identified in 72.5% of adult patients after CAA diagnosis. Antithrombotic agents, particularly aspirin, clopidogrel and heparin, were prescribed more frequently after CAA diagnosis. Among the prescribed medications, aspirin (75.8%), ß-blockers (48.3%), statins (47.6%), metformin (14.4%), sulfonylureas (14.4%) and isosorbide mononitrate (32.9%) were frequently observed in each category. CONCLUSIONS: Kawasaki disease was the main cause of CAA in pediatric patients, and coronary artery disease was the most common comorbidity in adult CAA patients. The most commonly used antithrombic agent after CAA diagnosis was aspirin in both adult and pediatric patients.

6.
J Am Chem Soc ; 141(36): 14190-14199, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31418268

RESUMO

Single-atom catalysts exhibit well-defined active sites and potentially maximum atomic efficiency. However, they are unsuitable for reactions that benefit from bimetallic promotion such as the oxygen evolution reaction (OER) in an alkaline medium. Here we show that a single-atom Co precatalyst can be in situ transformed into a Co-Fe double-atom catalyst for the OER. This catalyst exhibits one of the highest turnover frequencies among metal oxides. Electrochemical, microscopic, and spectroscopic data, including those from operando X-ray absorption spectroscopy, reveal a dimeric Co-Fe moiety as the active site of the catalyst. This work demonstrates double-atom catalysis as a promising approach for the development of defined and highly active OER catalysts.

7.
ACS Nano ; 13(10): 11853-11862, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31461618

RESUMO

Single-atom catalysts (SACs) have emerged as one of the most promising alternatives to noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). While SACs can offer notable benefits in terms of lowering overall catalyst cost, there is still room for improvement regarding catalyst activity. To this end, we designed and successfully fabricated an ORR electrocatalyst in which atomic clusters are embedded in an atomically dispersed Fe-N-C matrix (FeAC@FeSA-N-C), as shown by comprehensive measurements using aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS). The half-wave potential of FeAC@FeSA-N-C is 0.912 V (versus reversible hydrogen electrode (RHE)), exceeding that of commercial Pt/C (0.897 V), FeSA-N-C (0.844 V), as well as the half-wave potentials of most reported non-platinum-group metal catalysts. The ORR activity of the designed catalyst stems from single-atom active centers but is markedly enhanced by the presence of Fe nanoclusters, as confirmed by both experimental measurements and theoretical calculations.

8.
Adv Mater ; 31(41): e1903909, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31461181

RESUMO

NiFe-based layered double hydroxides (LDHs) are among the most efficient oxygen evolution reaction (OER) catalysts in alkaline medium, but their long-term OER stabilities are questionable. In this work, it is demonstrated that the layered structure makes bulk NiFe LDH intrinsically not stable in OER and the deactivation mechanism of NiFe LDH in OER is further revealed. Both operando electrochemical and structural characterizations show that the interlayer basal plane in bulk NiFe LDH contributes to the OER activity, and the slow diffusion of proton acceptors (e.g., OH- ) within the NiFe LDH interlayers during OER causes dissolution of NiFe LDH and therefore decrease in OER activity with time. To improve diffusion of proton acceptors, it is proposed to delaminate NiFe LDH into atomically thin nanosheets, which is able to effectively improve OER stability of NiFe LDH especially at industrial operating conditions such as elevated operating temperatures (e.g., at 80 °C) and large current densities (e.g., at 500 mA cm-2 ).

9.
Angew Chem Int Ed Engl ; 58(33): 11464-11468, 2019 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-31190443

RESUMO

Chiral aldehyde catalysis opens new avenues for the activation of simple amines. However, the lack of easy access to structurally diverse chiral aldehyde catalysts has hampered the development of this cutting-edge field. Herein, we report a Pd-catalyzed atroposelective C-H naphthylation with 7-oxabenzonorbornadienes for the preparation of axially chiral biaryls with excellent enantioselectivities (up to >99 % ee). This reaction is scalable and robust, which serves as a key step to provide a rapid access to axially chiral aldehyde catalysts through a three-step C-H functionalization sequence. These chiral aldehydes exhibit better activities and enantioselectivities than the previously reported organocatalysts in the asymmetric activation of glycine derived amides and dipeptides. Moreover, preliminary investigation also discloses that the aldehyde catalyst can effectively override the intrinsic facial selectivity of chiral dipeptide substrates, showcasing the strong chiral induction ability of this type of novel aldehyde catalysts.

10.
Science ; 364(6445): 1091-1094, 2019 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-31197014

RESUMO

Currently, the most active electrocatalysts for the conversion of CO2 to CO are gold-based nanomaterials, whereas non-precious metal catalysts have shown low to modest activity. Here, we report a catalyst of dispersed single-atom iron sites that produces CO at an overpotential as low as 80 millivolts. Partial current density reaches 94 milliamperes per square centimeter at an overpotential of 340 millivolts. Operando x-ray absorption spectroscopy revealed the active sites to be discrete Fe3+ ions, coordinated to pyrrolic nitrogen (N) atoms of the N-doped carbon support, that maintain their +3 oxidation state during electrocatalysis, probably through electronic coupling to the conductive carbon support. Electrochemical data suggest that the Fe3+ sites derive their superior activity from faster CO2 adsorption and weaker CO absorption than that of conventional Fe2+ sites.

11.
J Am Chem Soc ; 141(26): 10324-10330, 2019 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-31244186

RESUMO

Tin perovskite nanomaterial is one of the promising candidates to replace organic lead halide perovskites in lighting applications. Unfortunately, the performance of tin-based systems is markedly inferior to those featuring toxic Pb salts. In an effort to improve the emission quantum efficiency of nanoscale 2D layered tin iodide perovskites through fine-tuning the electronic property of organic ammonium salts, we came to unveil the relationship between dielectric confinement and the photoluminescent properties of tin iodide perovskite nanodisks. Our results show that increasing the dielectric contrast for organic versus inorganic layers leads to a bathochromic shift in emission peak wavelength, a decrease of exciton recombination time, and importantly a significant boost in the emission efficiency. Under optimized conditions, a leap in emission quantum yield to a record high 21% was accomplished for the nanoscale thienylethylammonium tin iodide perovskite (TEA2SnI4). The as-prepared TEA2SnI4 also possessed superior photostability, showing no sign of degradation under continuous irradiation (10 mW/cm2) over a period of 120 h.

12.
Adv Mater ; 31(28): e1900883, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31099042

RESUMO

Rationally designing active and durable catalysts for the oxygen evolution reaction (OER) is of primary importance in water splitting. Perovskite oxides (ABO3 ) with versatile structures and multiple physicochemical properties have triggered considerable interest in the OER. The leaching of A site cations can create nanostructures and amorphous motifs on the perovskite matrix, thus facilitating the OER process. However, selectively dissolving A site cations and simultaneously obtaining more active amorphous motifs derived from the B site cations remains a great challenge. Herein, a top-down strategy is proposed to transform bulk crystalline perovskite (LaNiO3 ) into a nanostructured amorphous hydroxide by FeCl3 post-treatment, resulting in an extremely low overpotential of 189 mV at 10 mA cm-2 . The top-down-constructed amorphous catalyst with a large surface area has dual NiFe active sites, where high-valence Ni3+ -based edge-sharing octahedral frameworks are surrounded by interstitial distorted Fe octahedra and contribute to the superior OER performance. This top-down strategy provides a valid way to design novel perovskite-derived catalysts.

13.
Angew Chem Int Ed Engl ; 58(22): 7445-7449, 2019 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-30951227

RESUMO

Hydroxide-exchange membrane fuel cells can potentially utilize platinum-group-metal (PGM)-free electrocatalysts, offering cost and scalability advantages over more developed proton-exchange membrane fuel cells. However, there is a lack of non-precious electrocatalysts that are active and stable for the hydrogen oxidation reaction (HOR) relevant to hydroxide-exchange membrane fuel cells. Here we report the discovery and development of Ni3 N as an active and robust HOR catalyst in alkaline medium. A supported version of the catalyst, Ni3 N/C, exhibits by far the highest mass activity and break-down potential for a PGM-free catalyst. The catalyst also exhibits Pt-like activity for hydrogen evolution reaction (HER) in alkaline medium. Spectroscopy data reveal a downshift of the Ni d band going from Ni to Ni3 N and interfacial charge transfer from Ni3 N to the carbon support. These properties weaken the binding energy of hydrogen and oxygen species, resulting in remarkable HOR activity and stability.

14.
ACS Cent Sci ; 5(3): 558-568, 2019 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-30937383

RESUMO

The oxygen evolution reaction (OER) is a key process that enables the storage of renewable energies in the form of chemical fuels. Here, we describe a catalyst that exhibits turnover frequencies higher than state-of-the-art catalysts that operate in alkaline solutions, including the benchmark nickel iron oxide. This new catalyst is easily prepared from readily available and industrially relevant nickel foam, and it is stable for many hours. Operando X-ray absorption spectroscopic data reveal that the catalyst is made of nanoclusters of γ-FeOOH covalently linked to a γ-NiOOH support. According to density functional theory (DFT) computations, this structure may allow a reaction path involving iron as the oxygen evolving center and a nearby terrace O site on the γ-NiOOH support oxide as a hydrogen acceptor.

15.
Yi Chuan ; 41(4): 318-326, 2019 Apr 20.
Artigo em Chinês | MEDLINE | ID: mdl-30992253

RESUMO

Breast cancer is one of the most common malignant tumors endangering women. It has been found that the subunits of the COP9 complex are closely related to the occurrence and development of malignant tumors, and the CSN4 subunit plays an important role in regulating the whole complex. In the breast cancer cell line MDA-MB-231, we successfully established a lentivirus-mediated CSN4-knockdown cell line. CCK8 cell proliferation assays and colony formation experiments confirmed that CSN4 knockdown significantly decreased the cellular proliferation rate. Cell cycle analysis showed that CSN4 knockdown increased sub-G1 population and induced apoptosis. In addition, Western blotting assays confirmed that CSN4 regulates the expression of CDK6 and Caspase3, suggesting that CSN4 modulates the proliferation and apoptosis of breast cancer cells by regulating the expression of CDK6 and Caspase3 genes and thereby tumorigenesis. This study has deepened our understanding of the molecular mechanism of apoptosis and cell growth in breast cancers, and further revealed the role and mechanism of CSN4 in cancer biology.


Assuntos
Proteínas Adaptadoras de Transdução de Sinal/genética , Apoptose , Neoplasias da Mama/genética , Neoplasias da Mama/patologia , Complexo do Signalossomo COP9/genética , Proliferação de Células , Caspase 3/metabolismo , Linhagem Celular Tumoral , Quinase 6 Dependente de Ciclina/metabolismo , Feminino , Regulação Neoplásica da Expressão Gênica , Técnicas de Silenciamento de Genes , Humanos
16.
Dalton Trans ; 48(21): 7122-7129, 2019 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-30839999

RESUMO

RuO2 has been generally considered as the most active catalyst for the oxygen evolution reaction (OER) to date and shows remarkably higher activity in an acidic electrolyte than under alkaline conditions. Nevertheless, the dynamic valence state and local structure of reactive centers (i.e., Ru) in both acidic and alkaline electrolytes have not been systematically investigated yet, especially through in situ approaches. Herein, we employed in situ X-ray absorption spectroscopy to study the dynamic valence state and local structure of RuO2 during the OER in both acidic and alkaline electrolytes. In the acidic electrolyte, the Ru center was reduced near the onset potential prior to launching the OER and was oxidized during the OER process, while the coordination numbers and the bond lengths of the Ru-O path also decreased as revealed by in situ EXAFS analysis. Besides, in the alkaline electrolyte, RuO2 showed a similar behavior as revealed under acidic conditions. These results provide an evident insight into the dynamic change of the RuO2 electrocatalyst during the OER.

17.
Nat Chem ; 11(3): 222-228, 2019 03.
Artigo em Inglês | MEDLINE | ID: mdl-30664719

RESUMO

The electrochemical reduction of CO2 could play an important role in addressing climate-change issues and global energy demands as part of a carbon-neutral energy cycle. Single-atom catalysts can display outstanding electrocatalytic performance; however, given their single-site nature they are usually only amenable to reactions that involve single molecules. For processes that involve multiple molecules, improved catalytic properties could be achieved through the development of atomically dispersed catalysts with higher complexities. Here we report a catalyst that features two adjacent copper atoms, which we call an 'atom-pair catalyst', that work together to carry out the critical bimolecular step in CO2 reduction. The atom-pair catalyst features stable Cu10-Cu1x+ pair structures, with Cu1x+ adsorbing H2O and the neighbouring Cu10 adsorbing CO2, which thereby promotes CO2 activation. This results in a Faradaic efficiency for CO generation above 92%, with the competing hydrogen evolution reaction almost completely suppressed. Experimental characterization and density functional theory revealed that the adsorption configuration reduces the activation energy, which generates high selectivity, activity and stability under relatively low potentials.

18.
J Am Chem Soc ; 141(7): 3014-3023, 2019 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-30673269

RESUMO

Oxygen electrochemistry plays a critical role in clean energy technologies such as fuel cells and electrolyzers, but the oxygen evolution reaction (OER) severely restricts the efficiency of these devices due to its slow kinetics. Here, we show that via incorporation of lithium ion into iridium oxide, the thus obtained amorphous iridium oxide (Li-IrO x) demonstrates outstanding water oxidation activity with an OER current density of 10 mA/cm2 at 270 mV overpotential for 10 h of continuous operation in acidic electrolyte. DFT calculations show that lithium incorporation into iridium oxide is able to lower the activation barrier for OER. X-ray absorption characterizations indicate that both amorphous Li-IrO x and rutile IrO2 own similar [IrO6] octahedron units but have different [IrO6] octahedron connection modes. Oxidation of iridium to higher oxidation states along with shrinkage in the Ir-O bond was observed by in situ X-ray absorption spectroscopy on amorphous Li-IrO x, but not on rutile IrO2 under OER operando conditions. The much more "flexible" disordered [IrO6] octahedrons with higher oxidation states in amorphous Li-IrO x as compared to the periodically interconnected "rigid" [IrO6] octahedrons in crystalline IrO2 are able to act as more electrophilic centers and thus effectively promote the fast turnover of water oxidation.

19.
J Am Chem Soc ; 140(49): 17263-17270, 2018 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-30441896

RESUMO

Composite electrocatalysts have exhibited high activities toward water electrolysis, but the catalytically active sites really in charge of the reaction are still debatable while the conventional in situ X-ray spectroscopies are not capable of conclusively identifying the interaction of these materials with the electrolyte because of the complexity of catalysis. In this work, by utilization of operando Kß1,3 high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) with a small incident angle, the operando quadrupole transition obviously showed that oxygen directly interacted with 3d orbitals of Co ions rather than that of Fe ions. Most importantly, Fe ions can promote the stabilization of the Co ions under a higher valent state during water oxidation, which may lead to a stable intermediate of reactant and its superior intrinsic activity. Accompanied by the first-principle calculations, the intermediates between 3d orbitals for surface Co ions and O 2p orbitals for the attaching hydroxide ions were ascribed to this orbital hybridization. Because of the unvaried structural features in conventional in situ techniques, operando HERFD-XAS revealed the remarkable change of chemical status to correlate with the orbital interaction rather than with the structural variation. This operando HERFD-XAS approach corresponding to the local orbital interaction in reactant/catalyst interface can potentially offer synergetic strategies toward realizing the chemical reactions or reaction pathways in various fields.

20.
Angew Chem Int Ed Engl ; 57(52): 17151-17155, 2018 12 21.
Artigo em Inglês | MEDLINE | ID: mdl-30411829

RESUMO

Biaryl atropisomers are of great importance in natural products, pharmaceuticals, and asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is a Pd-catalyzed atroposelective C-H allylation with tert-leucine as an efficient catalytic chiral transient auxiliary. A wide range of enantioenriched biaryl aldehydes were prepared in synthetically useful yields with excellent enantioselectivity (up to >99 % ee) through ß-O elimination. The reaction could be carried out on a gram scale without erosion of the ee value. A variety of axially chiral carboxylic acids could be obtained with high enantiopurity. The resulting axially chiral biaryl aldehydes and carboxylic acids might be used in asymmetric synthesis as chiral ligands and/or organocatalysts.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA