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1.
Nat Nanotechnol ; 2020 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-31988508

RESUMO

It has recently been shown that sulfur, a solid material in its elementary form S8, can stay in a supercooled state as liquid sulfur in an electrochemical cell. We establish that this newly discovered state could have implications for lithium-sulfur batteries. Here, through in situ studies of electrochemical sulfur generation, we show that liquid (supercooled) and solid elementary sulfur possess very different areal capacities over the same charging period. To control the physical state of sulfur, we studied its growth on two-dimensional layered materials. We found that on the basal plane, only liquid sulfur accumulates; by contrast, at the edge sites, liquid sulfur accumulates if the thickness of the two-dimensional material is small, whereas solid sulfur nucleates if the thickness is large (tens of nanometres). Correlating the sulfur states with their respective areal capacities, as well as controlling the growth of sulfur on two-dimensional materials, could provide insights for the design of future lithium-sulfur batteries.

2.
Adv Mater ; : e1906806, 2020 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-31950562

RESUMO

Oxygen evolution reaction (OER) catalysts that function efficiently in pH-neutral electrolyte are of interest for biohybrid fuel and chemical production. The low concentration of reactant in neutral electrolyte mandates that OER catalysts provide both the water adsorption and dissociation steps. Here it is shown, using density functional theory simulations, that the addition of hydrated metal cations into a Ni-Fe framework contributes water adsorption functionality proximate to the active sites. Hydration-effect-promoting (HEP) metal cations such as Mg2+ and hydration-effect-limiting Ba2+ into Ni-Fe frameworks using a room-temperature sol-gel process are incorporated. The Ni-Fe-Mg catalysts exhibit an overpotential of 310 mV at 10 mA cm-2 in pH-neutral electrolytes and thus outperform iridium oxide (IrO2 ) electrocatalyst by a margin of 40 mV. The catalysts are stable over 900 h of continuous operation. Experimental studies and computational simulations reveal that HEP catalysts favor the molecular adsorption of water and its dissociation in pH-neutral electrolyte, indicating a strategy to enhance OER catalytic activity.

3.
Nat Nanotechnol ; 15(2): 131-137, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31907442

RESUMO

To date, effective control over the electrochemical reduction of CO2 to multicarbon products (C ≥ 2) has been very challenging. Here, we report a design principle for the creation of a selective yet robust catalytic interface for heterogeneous electrocatalysts in the reduction of CO2 to C2 oxygenates, demonstrated by rational tuning of an assembly of nitrogen-doped nanodiamonds and copper nanoparticles. The catalyst exhibits a Faradaic efficiency of ~63% towards C2 oxygenates at applied potentials of only -0.5 V versus reversible hydrogen electrode. Moreover, this catalyst shows an unprecedented persistent catalytic performance up to 120 h, with steady current and only 19% activity decay. Density functional theory calculations show that CO binding is strengthened at the copper/nanodiamond interface, suppressing CO desorption and promoting C2 production by lowering the apparent barrier for CO dimerization. The inherent compositional and electronic tunability of the catalyst assembly offers an unrivalled degree of control over the catalytic interface, and thereby the reaction energetics and kinetics.

4.
J Org Chem ; 85(2): 622-632, 2020 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-31799847

RESUMO

An efficient Pd-catalyzed arylation of alkylpyridine based on the pyridinium activation strategy has been developed for synthesis of mixed aryl alkylpyridines. It was found that (1) the N-methyl group in the pyridinium salts acted as a transient activator and could be automatically departed after the reaction, (2) CuBr was an indispensable additive for achieving the C6-selective arylation, (3) the α-branched alkyl chain on the alkylpyridine greatly increased the yield of the product. Deuterium labelling experiment revealed that in the case of the α-branched alkylpyridine, the presence of CuBr completely inhibited the H/D exchange at the benzylic position and thus enabled the selective arylation at the C6 position. This protocol demonstrates a broad substrate scope, and with respect to both the aryl iodides and the α-branched alkylpyridine, the desired mixed aryl alkylpyridines were obtained in generally good to excellent yields.

5.
Infect Dis Poverty ; 8(1): 98, 2019 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-31791409

RESUMO

BACKGROUND: Aedes albopictus is a highly invasive mosquito species and a major vector of numerous viral pathogens. Many recent dengue fever outbreaks in China have been caused solely by the vector. Mapping of the potential distribution ranges of Ae. albopictus is crucial for epidemic preparedness and the monitoring of vector populations for disease control. Climate is a key factor influencing the distribution of the species. Despite field studies indicating seasonal population variations, very little modeling work has been done to analyze how environmental conditions influence the seasonality of Ae. albopictus. The aim of the present study was to develop a model based on available observations, climatic and environmental data, and machine learning methods for the prediction of the potential seasonal ranges of Ae. albopictus in China. METHODS: We collected comprehensive up-to-date surveillance data in China, particularly records from the northern distribution margin of Ae. albopictus. All records were assigned long-term (1970-2000) climatic data averages based on the WorldClim 2.0 data set. Machine learning regression tree models were developed using a 10-fold cross-validation method to predict the potential seasonal (or monthly) distribution ranges of Ae. albopictus in China at high resolution based on environmental conditions. The models were assessed based on sensitivity, specificity, and accuracy, using area under curve (AUC). WorldClim 2.0 and climatic and environmental data were used to produce environmental conduciveness (probability) prediction surfaces. Predicted probabilities were generated based on the averages of the 10 models. RESULTS: During 1998-2017, Ae. albopictus was observed at 200 out of the 242 localities surveyed. In addition, at least 15 new Ae. albopictus occurrence sites lay outside the potential ranges that have been predicted using models previously. The average accuracy was 98.4% (97.1-99.5%), and the average AUC was 99.1% (95.6-99.9%). The predicted Ae. albopictus distribution in winter (December-February) was limited to a small subtropical-tropical area of China, and Ae. albopictus was predicted to occur in northern China only during the short summer season (usually June-September). The predicted distribution areas in summer could reach northeastern China bordering Russia and the eastern part of the Qinghai-Tibet Plateau in southwestern China. Ae. albopictus could remain active in expansive areas from central to southern China in October and November. CONCLUSIONS: Climate and environmental conditions are key factors influencing the seasonal distribution of Ae. albopictus in China. The areas predicted to potentially host Ae. albopictus seasonally in the present study could reach northeastern China and the eastern slope of the Qinghai-Tibet Plateau. Our results present new evidence and suggest the expansion of systematic vector population monitoring activities and regular re-assessment of epidemic risk potential.

6.
Org Lett ; 21(23): 9425-9429, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31810112

RESUMO

A simple and efficient method for the synthesis of isoquinolone and isocoumarin derivatives is reported. The method for the first time provides a one-step divergent synthesis of important isoquinolone and isocoumarin skeletons from benzoic acid by switching the coupling partners. In addition, a reliable mechanism has been proposed on the basis of experimental investigations, including kinetic isotope effect experiments, 13C labeling experiments, time-tracking experiments, and competitive experiments, as well as DFT calculation studies.

7.
Parasit Vectors ; 12(1): 552, 2019 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-31752961

RESUMO

BACKGROUND: The Asian tiger mosquito, Aedes albopictus, is one of the 100 worst invasive species in the world and the vector for several arboviruses including dengue, Zika and chikungunya viruses. Understanding the population spatial genetic structure, migration, and gene flow of vector species is critical to effectively preventing and controlling vector-borne diseases. Little is known about the population structure and genetic differentiation of native Ae. albopictus in China. The aim of this study was to examine the patterns of the spatial genetic structures of native Ae. albopictus populations, and their relationship to dengue incidence, on a large geographical scale. METHODS: During 2016-2018, adult female Ae. albopictus mosquitoes were collected by human landing catch (HLC) or human-bait sweep-net collections in 34 localities across China. Thirteen microsatellite markers were used to examine the patterns of genetic diversity, population structure, and gene flow among native Ae. albopictus populations. The correlation between population genetic indices and dengue incidence was also examined. RESULTS: A total of 153 distinct alleles were identified at the 13 microsatellite loci in the tested populations. All loci were polymorphic, with the number of distinct alleles ranging from eight to sixteen. Genetic parameters such as PIC, heterozygosity, allelic richness and fixation index (FST) revealed highly polymorphic markers, high genetic diversity, and low population genetic differentiation. In addition, Bayesian analysis of population structure showed two distinct genetic groups in southern-western and eastern-central-northern China. The Mantel test indicated a positive correlation between genetic distance and geographical distance (R2 = 0.245, P = 0.01). STRUCTURE analysis, PCoA and GLS interpolation analysis indicated that Ae. albopictus populations in China were regionally clustered. Gene flow and relatedness estimates were generally high between populations. We observed no correlation between population genetic indices of microsatellite loci in Ae. albopictus populations and dengue incidence. CONCLUSION: Strong gene flow probably assisted by human activities inhibited population differentiation and promoted genetic diversity among populations of Ae. albopictus. This may represent a potential risk of rapid spread of mosquito-borne diseases. The spatial genetic structure, coupled with the association between genetic indices and dengue incidence, may have important implications for understanding the epidemiology, prevention, and control of vector-borne diseases.

8.
Proc Natl Acad Sci U S A ; 116(48): 23915-23922, 2019 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-31723041

RESUMO

Electrochemical reduction of CO2 to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO2 reduction reaction (CO2RR) at a cathode is always paired with the oxygen evolution reaction (OER) at an anode, the overall efficiency of electrical energy to chemical fuel conversion must consider the large energy barrier and sluggish kinetics of OER, especially in widely used electrolytes, such as the pH-neutral CO2-saturated 0.5 M KHCO3 OER in such electrolytes mostly relies on noble metal (Ir- and Ru-based) electrocatalysts in the anode. Here, we discover that by anodizing a metallic Ni-Fe composite foam under a harsh condition (in a low-concentration 0.1 M KHCO3 solution at 85 °C under a high-current ∼250 mA/cm2), OER on the NiFe foam is accompanied by anodic etching, and the surface layer evolves into a nickel-iron hydroxide carbonate (NiFe-HC) material composed of porous, poorly crystalline flakes of flower-like NiFe layer-double hydroxide (LDH) intercalated with carbonate anions. The resulting NiFe-HC electrode in CO2-saturated 0.5 M KHCO3 exhibited OER activity superior to IrO2, with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm2, respectively, and high stability for >120 h without decay. We paired NiFe-HC with a CO2RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO2 electrolyzer, achieving selective cathodic conversion of CO2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O2 The device showed a low cell voltage of 2.13 V and high electricity-to-chemical fuel efficiency of 59% at a current density of 10 mA/cm2.

9.
Chem Commun (Camb) ; 55(82): 12384-12387, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31559990

RESUMO

Herein, we report the first example of synthesis of N-substituted lactams via an acceptorless dehydrogenative coupling of diols with primary amines in one step, which was enabled by combining Ru3(CO)12 with a hybrid N-heterocyclic carbene-phosphine-phosphine ligand as the catalyst.

10.
ACS Appl Mater Interfaces ; 11(31): 27667-27676, 2019 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-31303002

RESUMO

Iron-nickel sulfide ((Ni,Fe)3S2) is one of the most promising bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media because of their metallic conductivity and low cost. However, the reported HER activity of (Ni,Fe)3S2 is still unsatisfactory. Herein, three-dimensional self-supported phosphorus-doped (Ni,Fe)3S2 nanosheet arrays on Ni foam (P-(Ni,Fe)3S2/NF) are synthesized by a simple one-step simultaneous phosphorization and sulfuration route, which exhibits dramatically enhanced HER activity as well as drives remarkable OER activity. The incorporation of P significantly optimized the hydrogen/water absorption free energy (ΔGH*/ΔGH2O*), enhanced electrical conductivity, and increased electrochemical surface area. Accordingly, the optimal P-(Ni,Fe)3S2/NF exhibits relatively low overpotentials of 98 and 196 mV at 10 mA cm-2 for HER and OER in 1 M KOH, respectively. Furthermore, an alkaline electrolyzer comprising the P-(Ni,Fe)3S2/NF electrodes needs a very low cell voltage of 1.54 V at 10 mA cm-2 and exhibits long-term stability and outperforms most other state-of-the-art electrocatalysts. The reported electrocatalyst activation approach by anion doping can be adapted for other transition-metal chalcogenides for water electrolysis, offering great promise for future applications.

11.
ACS Appl Mater Interfaces ; 11(31): 27964-27972, 2019 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-31294538

RESUMO

Exploring efficient bifunctional oxygen electrocatalysts is a critical element for developing high-power-density metal-air batteries. Here, we propose an interface and oxygen vacancy engineering strategy to integrate subtle lattice distortions, oxygen vacancies, and nanopores on the surface of NixCo1-xSe2-O interface nanocrystals, which exhibit efficient bifunctional catalytic performances for oxygen evolution and reduction. The results from X-ray absorption spectroscopy and electron spin resonance spectroscopy demonstrate that the defect structure can enlarge the number of active sites for electrocatalytic performances. Flexible Zn-air battery using NixCo1-xSe2-O as a cathode displays large specific capacity and remarkable stability even after twisting at any angle, thus showing potential for wearable and portable electronic device application. The implementation of our method provides a powerful strategy for preparing advanced catalysts for energy utilization.

12.
J Org Chem ; 84(14): 9151-9160, 2019 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-31273988

RESUMO

A selective catalytic system for the dehydrogenation of primary alcohols to carboxylic acids using a facial ruthenium complex generated in situ from the [Ru(COD)Cl2]n and a hybrid N-heterocyclic carbene (NHC)-phosphine-phosphine ligand (CPP) has been first reported. The facial coordination model was unveiled by NMR analysis of the reaction mixture. Such a fac-ruthenium catalyst system exhibited high catalytic activity and stability, and a high turnover number of 20 000 could be achieved with catalyst loading as low as 0.002 mol %. The exceedingly high catalyst stability was tentatively attributed to both the anchoring role of NHC and the hemi-lability of phosphines. The catalytic system also features a wide substrate scope. In particular, the facial coordination of CPP ligands was found to be beneficial for sterically hindered alcohols, and ortho-substituted benzylic alcohols and bulky adamantanyl methanol as well as cholesterol were all found to be viable dehydrogenation substrates.

13.
PLoS One ; 14(4): e0216001, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31022263

RESUMO

Amaranth plants contain large amounts of betalains, including betaxanthins and betacyanins. Amaranthin is a betacyanin, and its molecular structure and associated metabolic pathway differ from those of betanin in beet plants. The chlorophyll, carotenoid, betalain, and flavonoid contents in amaranth leaves were analyzed. The abundance of betalain, betacyanin, and betaxanthin was 2-5-fold higher in the red leaf sectors than in the green leaf sectors. Moreover, a transcriptome database was constructed for the red and green sectors of amaranth leaves harvested from 30-day-old seedlings. 22 unigenes were selected to analyze the expression profiles in the two leaf sectors. The RNA-sequencing data indicated that many unigenes are involved in betalain metabolic pathways. The potential relationships between diverse metabolic pathways and betalain metabolism were analyzed. The validation of the expression of 22 selected unigenes in a qRT-PCR assay revealed the genes that were differentially expressed in the two leaf sectors. Betalains were biosynthesized in specific tissues of the red sectors of amaranth leaves. Almost all of the genes related to betalain metabolism were identified in the transcriptome database, and the expression profiles were different between the red sectors and green sectors in the leaf. Amaranth plants consist of diverse metabolic pathways, and the betalain metabolic pathway is linked to a group of other metabolic pathways.


Assuntos
Amaranthus/genética , Betalaínas/metabolismo , Folhas de Planta/genética , Análise de Sequência de RNA/métodos , Carotenoides/metabolismo , Clorofila/metabolismo , Flavonoides/metabolismo , Regulação da Expressão Gênica de Plantas , Ontologia Genética , Genes de Plantas , Anotação de Sequência Molecular , Transcriptoma/genética
14.
Nat Commun ; 10(1): 982, 2019 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-30816110

RESUMO

Engineering catalytic sites at the atomic level provides an opportunity to understand the catalyst's active sites, which is vital to the development of improved catalysts. Here we show a reliable and tunable polyoxometalate template-based synthetic strategy to atomically engineer metal doping sites onto metallic 1T-MoS2, using Anderson-type polyoxometalates as precursors. Benefiting from engineering nickel and oxygen atoms, the optimized electrocatalyst shows great enhancement in the hydrogen evolution reaction with a positive onset potential of ~ 0 V and a low overpotential of -46 mV in alkaline electrolyte, comparable to platinum-based catalysts. First-principles calculations reveal co-doping nickel and oxygen into 1T-MoS2 assists the process of water dissociation and hydrogen generation from their intermediate states. This research will expand on the ability to improve the activities of various catalysts by precisely engineering atomic activation sites to achieve significant electronic modulations and improve atomic utilization efficiencies.

15.
Org Lett ; 21(4): 1002-1006, 2019 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-30730151

RESUMO

The first iridium-catalyzed oxidative alkeynylation of benzylamines with acrylates enabled by a new directing group pentafluorobenzoyl has been developed. The reaction proceeded efficiently in the presence of silver acetate as oxidant and chlorobenzene as solvent. A good range of benzylamines could be selectively monoalkenylated without interfering with further aza-Michael addition. The kinetic isotope effect experiments showed that C-H activation is not the rate-limiting step. In addition, a five-membered iridacycle species was isolated and established as the possible key intermediate.

16.
G3 (Bethesda) ; 9(4): 1037-1044, 2019 04 09.
Artigo em Inglês | MEDLINE | ID: mdl-30737238

RESUMO

Musk deer (Moschidae), whose secretion is an expensive and irreplaceable component of traditional medicine, have become endangered in the wild due to habitat fragmentation and over-exploitation. In recent years, China has had success in the artificial breeding of forest musk deer, thus relieving the pressure on wild populations. However, many farmed populations are experiencing degradation, and little genetic information is available for conservation management. In this study, we selected 274 individuals from three typical captive populations (originated from the Ta-pa Mountains (Tp), the midrange of the Qinling Mountains (Ql) and the Western Sichuan Plateau (WS), respectively) to evaluate the genetic variations. A total of more than 3.15 billion high-quality clean reads and 4.37 million high-quality SNPs were generated by RAD sequencing. Based on the analysis, we found that captive forest musk deer populations exhibit a relatively low level of genetic diversity. Ql displayed a higher level of genetic diversity than the Tp and WS populations. Tp and WS had experienced population bottlenecks in the past as inferred from the values of Tajima's D. There were high levels of heterozygote deficiency caused by inbreeding within the three populations. Population structure analysis suggested that the three populations have evolved independently, and a moderate amount of genetic differentiation has developed, although there was a low level of gene flow between the Ql and Tp populations. Furthermore, the average quantities of musk secreted by musk deer in the Tp and WS populations were significantly higher than that in the Ql population. The present genetic information should be considered in management plans for the conservation and utilization of musk deer from captive breeding.


Assuntos
Cruzamento/métodos , Cervos/genética , Variação Genética , Animais , China , Conservação dos Recursos Naturais , Filogenia , Polimorfismo de Nucleotídeo Único
17.
Adv Mater ; 31(11): e1804769, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30680808

RESUMO

Oxygen evolution reaction (OER) is a pivotal reaction in many technologies for renewable energy, such as water splitting, metal-air batteries, and regenerative fuel cells. However, this reaction is known to be kinetically sluggish and proceeds at rather high overpotential due to the universal scaling relationship, namely, the adsorption energies of intermediates are linearly correlated and cannot be optimized simultaneously. Several approaches have been proposed to break the scaling relationship by introducing additional active sites; however, positive experimental results are still absent. Herein, a different solution is suggested on the basis of dynamic tridimensional adsorption of the OER intermediates at NiO/NiFe layered double hydroxide intersection, by which the adsorption energy of each intermediate can be adjusted independently, so as to bypass the scaling relationship and achieve high catalytic performance. Experimentally, the OER overpotential is reduced to ≈205 mV at current density of 30 mA cm-2 , which represents the best performance achieved by state-of-the-art OER catalysts.

18.
J Org Chem ; 84(4): 2158-2168, 2019 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-30676029

RESUMO

Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.

19.
Nat Commun ; 9(1): 5289, 2018 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-30538249

RESUMO

Electrochemical intercalation of ions into the van der Waals gap of two-dimensional (2D) layered materials is a promising low-temperature synthesis strategy to tune their physical and chemical properties. It is widely believed that ions prefer intercalation into the van der Waals gap through the edges of the 2D flake, which generally causes wrinkling and distortion. Here we demonstrate that the ions can also intercalate through the top surface of few-layer MoS2 and this type of intercalation is more reversible and stable compared to the intercalation through the edges. Density functional theory calculations show that this intercalation is enabled by the existence of natural defects in exfoliated MoS2 flakes. Furthermore, we reveal that sealed-edge MoS2 allows intercalation of small alkali metal ions (e.g., Li+ and Na+) and rejects large ions (e.g., K+). These findings imply potential applications in developing functional 2D-material-based devices with high tunability and ion selectivity.

20.
Sci Adv ; 4(10): eaau6261, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-30345366

RESUMO

Atomic-level structure engineering can substantially change the chemical and physical properties of materials. However, the effects of structure engineering on the capacitive properties of electrode materials at the atomic scale are poorly understood. Fast transport of ions and electrons to all active sites of electrode materials remains a grand challenge. Here, we report the radical modification of the pseudocapacitive properties of an oxide material, Zn x Co1-x O, via atomic-level structure engineering, which changes its dominant charge storage mechanism from surface redox reactions to ion intercalation into bulk material. Fast ion and electron transports are simultaneously achieved in this mixed oxide, increasing its capacity almost to the theoretical limit. The resultant Zn x Co1-x O exhibits high-rate performance with capacitance up to 450 F g-1 at a scan rate of 1 V s-1, competing with the state-of-the-art transition metal carbides. A symmetric device assembled with Zn x Co1-x O achieves an energy density of 67.3 watt-hour kg-1 at a power density of 1.67 kW kg-1, which is the highest value ever reported for symmetric pseudocapacitors. Our finding suggests that the rational design of electrode materials at the atomic scale opens a new opportunity for achieving high power/energy density electrode materials for advanced energy storage devices.

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