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1.
Artículo en Inglés | MEDLINE | ID: mdl-39291640

RESUMEN

Proton exchange membrane fuel cells have strict requirements for the CO concentration in H2-rich fuel gas. Here, from the perspective of industrial practicability, a highly dispersed Pt catalyst (2-4 nm) supported on activated carbon (AC), which was modified by electronic promoters (K+) and structural promoters (isopropanol), is studied in detail. Compared with traditional metal oxide supports, the K-Pt/AC catalysts, which benefit from the tuned charge distribution, achieve a significant reduction of CO (from 1% to <0.1 ppb) under H2-rich conditions and show potential for used in large-scale industrial hydrogen purification. Experimental results and theoretical calculations reveal that the K atom, with its lower electronegativity, contributes to the shift of surface Pt2+ to a lower binding energy due to the presence of oxygen species on the AC surface. This facilitates oxygen activation and accelerates desorption of the CO2 product, thereby accelerating the reaction process and enabling the deep removal of CO in a hydrogen-rich atmosphere.

2.
Bioact Mater ; 40: 227-243, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38973993

RESUMEN

Limited cells and factors, inadequate mechanical properties, and necrosis of defects center have hindered the wide clinical application of bone-tissue engineering scaffolds. Herein, we construct a self-oxygenated 3D printed bioactive hydrogel scaffold by integrating oxygen-generating nanoparticles and hybrid double network hydrogel structure. The hydrogel scaffold possesses the characteristics of extracellular matrix; Meanwhile, the fabricated hybrid double network structure by polyacrylamide and CaCl2-crosslinked sodium carboxymethylcellulose endows the hydrogel favorable compressive strength and 3D printability. Furthermore, the O2 generated by CaO2 nanoparticles encapsulated in ZIF-8 releases steadily and sustainably because of the well-developed microporous structure of ZIF-8, which can significantly promote cell viability and proliferation in vitro, as well as angiogenesis and osteogenic differentiation with the assistance of Zn2+. More significantly, the synergy of O2 and 3D printed pore structure can prevent necrosis of defects center and facilitate cell infiltration by providing cells the nutrients and space they need, which can further induce vascular network ingrowth and accelerate bone regeneration in all areas of the defect in vivo. Overall, this work provides a new avenue for preparing cell/factor-free bone-tissue engineered scaffolds that possess great potential for tissue regeneration and clinical alternative.

3.
Phys Chem Chem Phys ; 25(37): 25581-25593, 2023 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-37721015

RESUMEN

Cu-based catalysts are a promising alternative to toxic mercury catalysts for acetylene hydrochlorination, but their effectiveness is limited due to the poor dispersion and deactivation caused by reduction, agglomeration, and carbon deposition. In this study, the activity and stability of carbon-supported CuCl2 catalysts were largely improved by introducing N-heterocyclic ketones. Remarkably, N-methyl-2-pyridone (NM2P) coordinated Cu-based catalysts exhibited over 95% acetylene conversion with better stability under the reaction conditions of T = 180 °C, GHSV (C2H2) of 80 h-1, and VHCl/VC2H2 = 1.2. The combined results of characterization and exhaustive density functional theory (DFT) calculations revealed that the O-Cu coordination between the NM2P ligand and Cu cation strengthened the combination of reactants and Cu active sites, lowering the key reaction energy barrier, thereby leading to high activity. Meanwhile, the addition of the NM2P ligand significantly inhibited the reduction of Cu2+ to Cu+/Cu0, avoiding the formation of CuCl aggregates and the coking caused by Cu0, enhancing the catalytic stability. Overall, our study provides important insights into the design and optimization of Cu-based catalysts for acetylene hydrochlorination.

4.
Nat Commun ; 14(1): 5108, 2023 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-37607934

RESUMEN

A great challenge for electrochemical CO2 reduction is to improve energy efficiency, which requires reducing overpotential while increasing product Faraday efficiency. Here, we designedly synthesize a hybrid electrocatalyst consisting of Fe nanoparticles, pyrrole-type Fe-N4 sites and less-oxygenated carbon supports, which exhibits a remarkable CO Faraday efficiency above 99% at an ultralow overpotential of 21 mV, reaching the highest cathode energy efficiency of 97.1% to date. The catalyst also can afford a CO selectivity nearly 100% with a high cathode energy efficiency (>90%) at least 100 h. The combined results of control experiments, in situ characterizations and theoretical calculations demonstrate that introducing Fe nanoparticles can reduce the overpotential by accelerating the proton transfer from CO2 to *COOH and lowering the free energy for *COOH formation, constructing pyrrole-type Fe-N4 sites and limiting oxygen species on carbon supports can increase CO Faraday efficiency through inhibiting the H2 evolution, thus achieving energy-efficient electrochemical CO2 reduction to CO.

5.
Inorg Chem ; 62(33): 13419-13427, 2023 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-37552876

RESUMEN

The utilization of Cu-based catalysts in CO2 conversion into valuable chemicals is of significant interest due to their potential in mitigating greenhouse gas emissions. However, the controllable design of Cu-based catalysts and the regulation of their mechanism remain challenging. In this study, a series of efficient Cu/L catalysts were prepared for this process, and the intrinsic influencing factors on the reaction routes were systematically revealed. Various techniques revealed that Cu particles in L-supported catalysts exhibited higher dispersion and formed Cu-O(OH)-K interfacial sites. However, with increasing Cu loading, the dispersion of Cu particles and the percentage of Cu-O(OH)-K interfaces decreased. Kinetic investigations revealed that the adsorption configuration and electronic structure of Cu species codetermined the reaction pathways and resulting selectivity. Cu/L catalysts possessing Cu-O(OH)-K interfaces and small particles demonstrated the preferential formation of formate species, promoting methanol formation. However, larger Cu particles generated carboxylate intermediates, resulting in higher CO selectivity..

6.
Org Lett ; 24(6): 1405-1411, 2022 02 18.
Artículo en Inglés | MEDLINE | ID: mdl-35138858

RESUMEN

A complementary copper-catalyzed and electrochemical aminosulfonylation of O-homoallyl benzimidates and N-alkenyl amidines with sodium sulfinates was developed. The terminal alkene substrate produced sulfone-containing 1,3-oxazines and tetrahydropyrimidines in the presence of Cu(OAc)2, Ag2CO3, and DPP, and under similar reaction conditions, sulfonylated tetrahydro-1,3-oxazepines were prepared from 1-aryl-substituted O-homoallyl benzimidates in moderate to good yields. For certain electron-rich 1,1-diaryl-substituted alkene substrates, the corresponding tetrahydro-1,3-oxazepines could also be obtained in similar or even higher yields via a green electrochemical technique.

7.
Phys Chem Chem Phys ; 22(5): 2849-2857, 2020 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-31967628

RESUMEN

A green catalyst for acetylene hydrochlorination yielding a VCM is presented using imidazole as a single component metal-free catalyst. The mechanisms and reactivities of imidazole-catalyzed acetylene hydrochlorination have been investigated by combined computational and experimental studies. The electronic effects of ortho-substituents on the reactivities have also been investigated. Through theoretical calculations and experimental studies, the nitrogen-atom including a lone pair active site of single component imidazole for metal-free acetylene hydrochlorination is proposed. It is suggested that the nitrogen-atom including a lone pair of imidazole adsorbs an HCl molecule to form an imidazole-HCl complex, which serves as the active catalyst to participate in the reaction process of acetylene hydrochlorination. Besides, the results show that C2H2 assists in the electrophilic addition of HCl, undergoing an almost planar six-membered ring transition state. Computational studies on the ortho-substitution of the active sites will have an important impact on the catalytic efficiency.

8.
ACS Appl Mater Interfaces ; 11(28): 25100-25107, 2019 Jul 17.
Artículo en Inglés | MEDLINE | ID: mdl-31260243

RESUMEN

CuZn alloy, regarded as the active sites, shows excellent catalytic activity for the reverse water gas shift reaction, whereas the incorporation of N atoms, especially pyridinic N, can greatly improve its catalytic properties because of the strong promotion capacity for adsorption and activation of CO2 molecules. Herein, the synthesis strategy involving Cu-doped Zn-based metal-organic frameworks is utilized to prepare CuZn alloy coated in an N-doped carbon shell. The excellent catalytic ability for CO2 transformation originates from the synergistic catalytic effect between CuZn alloy and pyridinic N. The strong adsorption and activation capacity for CO2 of pyridinic N is ascribed to the lone pair of electrons on the N atom and the high electron density in its vicinity.

9.
Molecules ; 24(13)2019 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-31248058

RESUMEN

The objective of this study was to develop an ultrasonic-assisted procedure for the extraction of total phenolics from Citrus aurantium L. blossoms (CAB) and evaluate the free radical scavenging activity and anti-HMG-CoA reductase activity of the total phenolics. In this work, a Box- Behnken design based on single-factor experiments was used to explore the optimum extraction process. Under the optimum conditions (extraction solvent 70.31% ethanol, extraction temperature 61.94 °C, extraction time 51.73 min, and liquid-to-solid ratio 35.63 mL/g), the extraction yield of total phenolics was 95.84 mg gallic acid equivalents (GAE)/g dry matter (DM), which was highly consistent with the theoretical value (96.12 mg GAE/g DM). The higher contents of total phenolics and five main phenolic compounds obtained from the optimized ultrasonic-assisted extraction (UAE) proved its efficiency when compared with conventional heat reflux extraction (HRE). The total phenolic extract showed excellent free radical scavenging properties against 1,1-diphenyl-2-picrylhydrazyl radical (DPPH·), 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulphonic acid) radical (ABTS+·), hydroxyl radical (·OH) and superoxide anion radical (·O2-), with IC50 values of 197.007, 83.878, 218.643, and 158.885 µg/mL, respectively; the extracts also showed good inhibition of ß-hydroxy-ß-methylglutaryl-CoA reductase (HMG-CoA reductase) activity, with an IC50 value of 117.165 µg/mL. Total phenolics from CAB could be a potential source of natural free radical scavenger and HMG-CoA reductase inhibitor.


Asunto(s)
Citrus/química , Depuradores de Radicales Libres/química , Depuradores de Radicales Libres/farmacología , Inhibidores de Hidroximetilglutaril-CoA Reductasas/química , Inhibidores de Hidroximetilglutaril-CoA Reductasas/farmacología , Fenoles/química , Fenoles/farmacología , Análisis de Varianza , Cromatografía Líquida de Alta Presión , Depuradores de Radicales Libres/aislamiento & purificación , Inhibidores de Hidroximetilglutaril-CoA Reductasas/aislamiento & purificación , Extracción Líquido-Líquido , Fenoles/aislamiento & purificación , Extractos Vegetales/química , Extractos Vegetales/aislamiento & purificación , Extractos Vegetales/farmacología , Ondas Ultrasónicas
10.
Sci Rep ; 7: 39789, 2017 01 04.
Artículo en Inglés | MEDLINE | ID: mdl-28051131

RESUMEN

Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

11.
ACS Appl Mater Interfaces ; 8(8): 5224-33, 2016 Mar 02.
Artículo en Inglés | MEDLINE | ID: mdl-26854574

RESUMEN

Mn2O3-doped Fe2O3 hexagonal microsheets were prepared for the low-temperature selective catalytic reduction (SCR) of NO with NH3. These hexagonal microsheets were characterized by SEM, TEM, XRD, BET, XPS, NH3-TPD, H2-TPR, and in situ DRIFT and were shown to exhibit a considerable uniform hexagonal microsheet structure and excellent low temperature SCR efficiency. When doped with different Mn molar ratios, Mn2O3 was detected in the Fe2O3 hexagonal microsheets based on the XRD results without the presence of other MnOX species. In addition, the hexagonal microsheets with a Mn/Fe molar ratio of 0.2 showed the best SCR removal performance among the materials, where a 98% NO conversion ratio at 200 °C at a space velocity of 30,000 h(-1) was obtained. Meanwhile, excellent tolerances to H2O and SO2, as well as high thermal stability, were obtained in Mn2O3-doped Fe2O3 hexagonal microsheets. Moreover, on the basis of the XPS and in situ DRIFT results, it can be suggested that coupled Mn2O3 nanocrystals played a key role at low temperatures and produced a possible redox reaction mechanism in the SCR process.

12.
Bioresour Technol ; 183: 93-100, 2015 May.
Artículo en Inglés | MEDLINE | ID: mdl-25725407

RESUMEN

Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases.


Asunto(s)
Aviación , Biocombustibles , Biotecnología/métodos , Aceite de Ricino/química , Níquel/química , Agua/química , Ácidos/química , Catálisis , Hidrógeno/química , Propilaminas/química , Espectroscopía de Protones por Resonancia Magnética , Silanos/química , Dióxido de Silicio/química , Temperatura , Zeolitas/química
13.
Mitochondrial DNA ; 24(3): 255-6, 2013 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-23316785

RESUMEN

Here, we sequenced the complete mitochondrial genome of Spilornis cheela (Falconiformes, Accipitridae), which is considered as endemic raptor species and listed in the second category of National Key Protected Wild Animals in China. The genome is 18,291 bp in size. Its gene arrangement pattern was identical with that of Spizaetus alboniger. We compared the mitochondrial genome of S. cheela with that of S. alboniger. Nucleotide sequence similarity between the two whole mitochondrial genomes was 84.34%, and the relatively low similarity seems to indicate that the two species are distinctly separated on the species level. The information on the mitochondrial genome comparison of the two species is discussed in detail in this paper.


Asunto(s)
Falconiformes/genética , Genoma Mitocondrial , Animales , China , Falconiformes/clasificación , Especificidad de la Especie
14.
Mitochondrial DNA ; 24(2): 86-8, 2013 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-22950669

RESUMEN

The complete mitochondrial genome sequence of Gekko swinhonis was determined in this paper. The genome was 16,818 bp in length and contained 13 protein-coding genes, 2 rRNA genes, 22 tRNA genes, and 1 control region (CR). The gene composition and order of G. swinhonis were similar to most other squamate reptiles. The overall base composition of the genome in descending order was 31.35% A, 27. 71% C, 26.28% T, and 14.67% G, with a slight AT bias of 57.62%. CR is located between the tRNA-Pro and tRNA-Phe genes and is 1456 bp in length; some tandem repeat sequences and conserved elements (TAS, CSB1-3) were found in the CR.


Asunto(s)
ADN Mitocondrial/genética , Lagartos/genética , Animales
15.
Mitochondrial DNA ; 23(4): 318-20, 2012 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-22708853

RESUMEN

In this paper, we sequenced the complete mitochondrial genome of Kallima inachus (Lepidoptera: Nymphalidae: Nymphalinae), which is considered a rare species in China. The genome is 15,183 bp in size. Its gene arrangement pattern was identical with those of Argynnis hyperbius. We compared the mitochondrial genome of K. inachus with that of A. hyperbius. Nucleotide sequence similarity between the two whole mitochondrial genomes was 85.92%, and the relatively low similarity seems to indicate that the two species are distinctly separated on the species level. The information on the mitochondrial genome comparison of the two species is discussed in detail in this paper.


Asunto(s)
Mariposas Diurnas/genética , Especies en Peligro de Extinción , Genoma de los Insectos/genética , Genoma Mitocondrial/genética , Lepidópteros/genética , Animales , Secuencia de Bases , Mariposas Diurnas/clasificación , China , ADN Mitocondrial/genética , Orden Génico , Proteínas de Insectos/genética , Lepidópteros/clasificación , Especificidad de la Especie
16.
Mitochondrial DNA ; 23(4): 315-7, 2012 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-22708858

RESUMEN

The 16,585 base pairs mitochondrial genome of Shinisaurus crocodilurus was determined by using PCR amplification and DNA sequencing. To determine the phylogenetic position of S. crocodilurus with related species within Squamata, the phylogenetic tree was reconstructed with the concatenated nucleotide sequences of the 12 heavy-strand-encoded protein genes. Phylogenetic analyses based on maximum parsimony and Bayesian inference methods consistently support that the S. crocodilurus was closely related to the Helodermatidae within a monophyletic Anguimorpha group. And the result here contradicted the monophyly of Varanoidea (Varanidae + Helodermatidae). In addition, the Gekkonidae was found to possess a basal phylogenetic position within squamata and the traditional hypothesis of monophyletic lineages of Iguania and Scleroglossa was not supported in this study.


Asunto(s)
Genoma Mitocondrial/genética , Lagartos/genética , Filogenia , Análisis de Secuencia de ADN/métodos , Animales , Teorema de Bayes , ADN Mitocondrial/genética , Lagartos/clasificación , Datos de Secuencia Molecular , Proteínas/genética
17.
Zoolog Sci ; 29(6): 384-9, 2012 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-22639809

RESUMEN

Black-spotted and red-spotted tokay geckos are distributed in different regions and have significant differences in morphological appearance, but have been regarded as the same species, Gekko gecko, in taxonomy. To determine whether black-spotted and red-spotted tokay geckos are genetically differentiated, we sequenced the entire mitochondrial cytochrome b gene (1147 bp) from 110 individuals of Gekko gecko collected in 11 areas including Guangxi China, Yunnan China, Vietnam, and Laos. In addition, we performed karyotypic analyses of black-spotted tokay geckos from Guangxi China and red-spotted tokay geckos from Laos. These phylogenetic analyses showed that black-spotted and red-spotted tokay geckos are divided into two branches in molecular phylogenetic trees. The average genetic distances are as follows: 0.12-0.47% among six haplotypes in the black-spotted tokay gecko group, 0.12-1.66% among five haplotypes in the red-spotted tokay gecko group, and 8.76-9.18% between the black-spotted and red-spotted tokay geckos, respectively. The karyotypic analyses showed that the karyotype formula is 2n = 38 = 8m + 2sm + 2st + 26t in red-spotted tokay geckos from Laos compared with 2n = 38 = 8m + 2sm + 28t in black-spotted tokay geckos from Guangxi China. The differences in these two kinds of karyotypes were detected on the 15th chromosome. The clear differences in genetic levels between black-spotted and red-spotted tokay geckos suggest a significant level of genetic differentiation between the two.


Asunto(s)
Citocromos b/genética , ADN Mitocondrial/genética , Regulación de la Expresión Génica/fisiología , Variación Genética , Cariotipo , Lagartos/genética , Animales , Citocromos b/metabolismo , Filogenia
18.
Mitochondrial DNA ; 23(1): 37-8, 2012 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-22295866

RESUMEN

In this paper, we sequenced the complete mitochondrial genome of the Manis pentadactyla (Pholidota: Manidae), which is considered as an endemic species in China. It is listed as a vulnerable species by the International Union for Conservation of Nature and Natural Resources Red List and also an endangered species in China. The genome is 16,578 bp in size. Its gene arrangement pattern was identical with those of Manis tetradactyla. We compared the mitochondrial genome of M. pentadactyla with that of the M. tetradactyla. Nucleotide sequence similarity between the two whole mitochondrial genomes was 79.30%, and the relatively low similarity seems to indicate that the two species are distinctly separated on the species level. The information on the mitochondrial genome comparison of the two species was discussed in detail in this paper.


Asunto(s)
ADN Mitocondrial/genética , Genoma , Mamíferos/genética , Animales , Secuencia de Bases , Cartilla de ADN , Mamíferos/clasificación , Filogenia
19.
J Environ Manage ; 92(11): 2939-43, 2011 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-21813231

RESUMEN

The effect of the surfactant template cetyltrimethylammonium bromide (CTAB) in MCM-41 on the adsorption of aniline was investigated. Various MCM-41 samples were prepared by controlling template removal using an extraction method. The samples were then used as adsorbents for the removal of aniline from aqueous solution. The results showed that the MCM-41 samples with the template partially removed (denoted as C-MCM-41) exhibited better adsorption performance than MCM-41 with the template completely removed (denoted as MCM-41). The reason for this difference may be that the C-MCM-41 samples had stronger hydrophobic properties and selectivity for aniline because of the presence of the template. The porosity and cationic sites generated by the template play an important role in the adsorption process. The optimal adsorbent with moderate template was achieved by changing the ratio of extractant; it has the potential for promising applications in the field of water pollution control.


Asunto(s)
Compuestos de Anilina/aislamiento & purificación , Carcinógenos/aislamiento & purificación , Dióxido de Silicio/síntesis química , Eliminación de Residuos Líquidos/métodos , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Concentración de Iones de Hidrógeno , Cinética , Temperatura
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