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Magnetic covalent organic framework nanocomposite denoted as Fe3O4@TAPB-Tp with core-shell structure was fabricated via a simple template-mediated precipitation polymerization method at mild conditions. The polyimine network shell was created through the polymerization of 1,3,5-tris(4-aminophenyl)-benzene (TAPB) and 1,3,5-triformyl-phloroglucinol (Tp) in tetrahydrofuran (THF) by the Schiff-base reaction. Featuring with large specific surface area (163.19 m2 g-1), good solution dispersibility, and high stability, the obtained Fe3O4@TAPB-Tp exhibited high adsorption capacities and fast adsorption for zearalenone and its derivatives (ZEAs). The adsorption isotherms showed multilayer adsorption dominated at low concentration and monolayer adsorption at high concentration between the interface of ZEAs and Fe3O4@TAPB-Tp. With the Fe3O4@TAPB-Tp as sorbent, a magnetic solid-phase extraction-ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was established for simultaneous adsorption and detection of five ZEAs in complex samples. The proposed method displayed favorable linearity, low limits of detection (0.003 ~ 0.018 µg kg-1), and good repeatability (2.37~10.4%). The developed method has been applied for real sample analysis, with recoveries of 81.27~90.26%. These results showed that Fe3O4@TAPB-Tp has a good application potential for the adsorption of ZEAs in food samples. Magnetic covalent organic framework nanocomposite (Fe3O4@TAPB-Tp) were quickly fabricated at mild conditions and used as effective adsorbent for magnetic solid-phase extraction of zearalenone and its derivatives (ZEAs) from food samples prior to ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis.
Assuntos
Nanopartículas de Magnetita/química , Estruturas Metalorgânicas/química , Micotoxinas/análise , Zearalenona/análise , Adsorção , Animais , Derivados de Benzeno/química , Cromatografia Líquida de Alta Pressão , Ovos/análise , Contaminação de Alimentos/análise , Limite de Detecção , Fenômenos Magnéticos , Leite/química , Micotoxinas/química , Micotoxinas/isolamento & purificação , Nanocompostos/química , Floroglucinol/análogos & derivados , Floroglucinol/química , Polimerização , Extração em Fase Sólida/métodos , Espectrometria de Massas em Tandem , Zea mays , Zearalenona/análogos & derivados , Zearalenona/isolamento & purificaçãoRESUMO
We herein report a new catalytic method for intermolecular olefin aminofluorination using earth-abundant iron catalysts and nucleophilic fluoride ion. This method tolerates a broad range of unfunctionalized olefins, especially nonstyrenyl olefins that are incompatible with existing olefin aminofluorination methods. This new iron-catalyzed process directly converts readily available olefins to internal vicinal fluoro carbamates with high regioselectivity (N vs F), many of which are difficult to prepare using known methods. Preliminary mechanistic studies demonstrate that it is possible to exert asymmetric induction using chiral iron catalysts and that both an iron-nitrenoid and carbocation species may be reactive intermediates.
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Alcenos/química , Fluoretos/química , Halogenação , Ferro/química , Catálise , EstereoisomerismoRESUMO
Reported herein is a new iron-catalyzed diastereoselective olefin diazidation reaction which occurs at room temperature (1-5â mol% of catalysts and d.r.â values of up to >20:1). This method tolerates a broad range of both unfunctionalized and highly functionalized olefins, including those that are incompatible with existing methods. It also provides a convenient approach to vicinal primary diamines as well as other synthetically valuable nitrogen-containing building blocks which are difficult to obtain with alternative methods. Preliminary mechanistic studies suggest that the reaction may proceed through a new mechanistic pathway in which both Lewis acid activation and iron-enabled redox-catalysis are crucial for selective azido-group transfer.
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Alcenos/química , Azidas/química , Ferro/química , CatáliseRESUMO
An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.
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Alcenos/química , Hidroxilaminas/química , Ferro/química , Oxidantes/química , Aminação , Catálise , EstereoisomerismoRESUMO
BACKGROUND: In recent years, China has experienced tremendous growth in its pharmaceutical industry. Both the Chinese government and private investors are motivated to invest into pharmaceutical research and development (R&D). However, studies regarding the different behaviors of public and private investment in pharmaceutical R&D are scarce. Therefore, this paper aims to investigate the current situation of public funding and private investment into Chinese pharmaceutical R&D. METHODS: The primary data used in the research were obtained from the China High-tech Industry Statistics Yearbook (2002-2012) and China Statistical Yearbook of Science and Technology (2002-2012). We analyzed public funding and private investment in five aspects: total investment in the industry, funding sources of the whole industry, differences between provinces, difference in subsectors, and private equity/venture capital investment. RESULTS: The vast majority of R&D investment was from private sources. There is a significantly positive correlation between public funding and private investment in different provinces of China. However, public funding was likely to be invested into less developed provinces with abundant natural herbal resources. Compared with the chemical medicine subsector, traditional Chinese medicine and biopharmaceutical subsectors obtained more public funding. Further, the effect of the government was focused on private equity and venture capital investment although private fund is the mainstream of this type of investment. CONCLUSIONS: Public funding and private investment play different but complementary roles in pharmaceutical R&D in China. While being less than private investment, public funding shows its significance in R&D investment. With rapid growth of the industry, the pharmaceutical R&D investment in China is expected to increase steadily from both public and private sources.
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Indústria Farmacêutica/economia , Financiamento Governamental/economia , Investimentos em Saúde/economia , Setor Privado/economia , Setor Público/economia , Pesquisa/economia , China , Indústria Farmacêutica/tendências , Financiamento Governamental/tendências , Investimentos em Saúde/tendências , Setor Privado/tendências , Setor Público/tendências , Pesquisa/tendênciasRESUMO
The sterile insect technique is based on the overflooding of a target population with released sterile males inducing sterility in the wild female population. It has proven to be effective against several insect pest species of agricultural and veterinary importance and is under development for Aedes mosquitoes. Here, we show that the release of sterile males at high sterile male to wild female ratios may also impact the target female population through mating harassment. Under laboratory conditions, male to female ratios above 50 to 1 reduce the longevity of female Aedes mosquitoes by reducing their feeding success. Under controlled conditions, blood uptake of females from an artificial host or from a mouse and biting rates on humans are also reduced. Finally, in a field trial conducted in a 1.17 ha area in China, the female biting rate is reduced by 80%, concurrent to a reduction of female mosquito density of 40% due to the swarming of males around humans attempting to mate with the female mosquitoes. This suggests that the sterile insect technique does not only suppress mosquito vector populations through the induction of sterility, but may also reduce disease transmission due to increased female mortality and lower host contact.
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Aedes , Infertilidade Masculina , Humanos , Feminino , Masculino , Animais , Camundongos , Reprodução , Comunicação Celular , InsetosRESUMO
BACKGROUND AND OBJECTIVE: Neuropathic pain (NeP) induced dysbiosis of intestinal microbiota in chronic constriction injury (CCI) rats. Emodin has analgesic effect but the detailed mechanism is not clear at the present time. This study aims to explore the underling mechanism of action of emodin against NeP with in CCI model. METHODS: Male SD rats (180-220 g) were randomly divided into three groups: sham group, CCI group, and emodin group. Behavioral tests were performed to evaluate the therapeutic effects of emodin on CCI model. Feces and spinal cords of all rats were collected 15 days after surgery. 16S rDNA sequencing, untargeted metabolomics, qPCR and ELISA were performed. RESULTS: Mechanical withdrawal thresholds (MWT), thermal withdrawal latency (TWL) and Sciatic functional index (SFI) in emodin group were significantly higher than CCI group (P < 0.05). Emodin not only inhibited the expression of pro-inflammatory cytokines in the spinal cords and colonic tissue, but also increased the expression of tight junction protein in colonic tissue. 16S rDNA sequencing showed that emodin treatment changed the community structure of intestinal microbiota in CCI rats. Untargeted metabolomics analysis showed that 33 differential metabolites were screened out between CCI group and emodin group. After verification, we found that emodin increased the level of S-adenosylmethionine (SAM) and Histamine in the spinal cord of CCI rats. CONCLUSION: Emodin was effective in relieving neuropathic pain, which is linked to inhibition inflammatory response, increasing the proportion of beneficial bacteria and beneficial metabolites.
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Emodina , Microbiota , Neuralgia , Ratos , Masculino , Animais , Ratos Sprague-Dawley , Emodina/farmacologia , Emodina/uso terapêutico , Analgésicos/farmacologia , Analgésicos/uso terapêutico , Medula Espinal , Neuralgia/metabolismo , DNA Ribossômico/metabolismoRESUMO
A novel chemiluminescence (CL) system was established for the determinations of daidzein in pharmaceutical preparations and to assess its ability to scavenge hydroxyl radicals. It was shown that a strong CL signal generated when eosin Y was mixed with Fenton reagent was decreased significantly when daidzein was added to the reaction system due to partial scavenging of the hydroxyl radicals in the solution. The extent of decrease in the CL intensity had a good stoichiometric relationship with the daidzein concentration. Based on this, we developed a new method for the determination of daidzein, using a flow-injection chemiluminescence (FI-CL) technique. Under the optimal conditions, the linear range of daidzein concentration was 8.0 × 10(-8) -3.0 × 10(-6) mol/L (R = 0.9982), with a detection limit of 9.0 × 10(-9) mol/L (S:N = 3), and the RSD was 5.8% for 1.0 × 10(-6) mol/L daidzein (n = 11). This method was successfully used in the determination of daidzein in tablets and for evaluation of the hydroxyl radical-scavenging capacity of daidzein. The possible reaction mechanism of the CL system is discussed.
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Sequestradores de Radicais Livres/análise , Radical Hidroxila/análise , Isoflavonas/análise , Medições Luminescentes/métodos , Preparações Farmacêuticas/análiseRESUMO
OBJECTIVE: Numerous studies have demonstrated the close relationship between chronic stress and blood pressure (BP). Hypertensive subjects exhibit exaggerated reactions to stress, especially higher BP. The mechanisms by which stress affects pre-existing hypertension still need to be explored. Danzhi Xiaoyao Powder (DP), a historical traditional Chinese medicine formula, is a promising treatment for BP control in hypertensive patients under stress. The present study investigated the metabolomic disruption caused by chronic stress and the treatment effect and mechanism of DP. METHODS: Spontaneously hypertensive rats (SHRs) were subjected to chronic restraint stress (CRS) for 4 weeks. BP was measured via the tail-cuff method, and anxiety-like behavior was quantified using the elevated-plus-maze test. Meanwhile, DP was administered intragastrically, and its effects were observed. Global metabolomic analysis was performed using ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry, followed by multivariate statistical analysis to detect differential metabolites and pathways. RESULTS: DP alleviated the CRS-induced increase in BP and anxiety-like behavior. Systematic metabolic differences were found among the three study groups. A total of 29 differential plasma metabolites were identified in both positive- and negative-ion modes. These metabolites were involved in triglyceride metabolism, amino acid (phenylalanine, tryptophan, and glycine) metabolism, and steroid hormone pathways. CONCLUSION: These findings expose the metabolomic disturbances induced by chronic stress in SHRs and suggest an innovative treatment for this disorder.
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Medicamentos de Ervas Chinesas , Medicina Tradicional Chinesa , Animais , Cromatografia Líquida de Alta Pressão , Medicamentos de Ervas Chinesas/farmacologia , Humanos , Pós , Ratos , Ratos Endogâmicos SHRRESUMO
OBJECTIVE: Glioma is the most common primary malignancy of the adult central nervous system (CNS), with a poor prognosis and no effective prognostic signature. Since late 2019, the world has been affected by the rapid spread of SARS-CoV-2 infection. Research on SARS-CoV-2 is flourishing; however, its potential mechanistic association with glioma has rarely been reported. The aim of this study was to investigate the potential correlation of SARS-CoV-2-related genes with the occurrence, progression, prognosis, and immunotherapy of gliomas. METHODS: SARS-CoV-2-related genes were obtained from the human protein atlas (HPA), while transcriptional data and clinicopathological data were obtained from The Cancer Genome Atlas (TCGA) and Chinese Glioma Genome Atlas (CGGA) databases. Glioma samples were collected from surgeries with the knowledge of patients. Differentially expressed genes were then identified and screened, and seven SARS-CoV-2 related genes were generated by LASSO regression analysis and uni/multi-variate COX analysis. A prognostic SARS-CoV-2-related gene signature (SCRGS) was then constructed based on these seven genes and validated in the TCGA validation cohort and CGGA cohort. Next, a nomogram was established by combining critical clinicopathological data. The correlation between SCRGS and glioma related biological processes was clarified by Gene set enrichment analysis (GSEA). In addition, immune infiltration and immune score, as well as immune checkpoint expression and immune escape, were further analyzed to assess the role of SCRGS in glioma-associated immune landscape and the responsiveness of immunotherapy. Finally, the reliability of SCRGS was verified by quantitative real-time polymerase chain reaction (qRT-PCR) on glioma samples. RESULTS: The prognostic SCRGS contained seven genes, REEP6, CEP112, LARP4B, CWC27, GOLGA2, ATP6AP1, and ERO1B. Patients were divided into high- and low-risk groups according to the median SARS-CoV-2 Index. Overall survival was significantly worse in the high-risk group than in the low-risk group. COX analysis and receiver operating characteristic (ROC) curves demonstrated excellent predictive power for SCRGS for glioma prognosis. In addition, GSEA, immune infiltration, and immune scores indicated that SCRGS could potentially predict the tumor microenvironment, immune infiltration, and immune response in glioma patients. CONCLUSIONS: The SCRGS established here can effectively predict the prognosis of glioma patients and provide a potential direction for immunotherapy.
Assuntos
COVID-19 , Glioma , ATPases Vacuolares Próton-Translocadoras , Adulto , Humanos , SARS-CoV-2/genética , Reprodutibilidade dos Testes , COVID-19/genética , Imunoterapia , Glioma/genética , Glioma/terapia , Microambiente Tumoral , Ciclofilinas , Proteínas do Olho , Proteínas de MembranaRESUMO
The use of seawater to prepare geopolymers has attracted significant research attention; however, the ions in seawater considerably influence the properties of the resulting geopolymers. This study investigated the effects of magnesium salts and alkaline solutions on the microstructure and properties of ground-granulated-blast-furnace-slag-based geopolymers. The magnesium salt-free Na2SiO4-activatied geopolymer exhibited a much higher 28 d compressive strength (63.5 MPa) than the salt-free NaOH-activatied geopolymer (31.4 MPa), with the former mainly containing an amorphous phase (C-(A)-S-H gel) and the latter containing numerous crystals. MgCl2·6H2O addition prolonged the setting times and induced halite and Cl-hydrotalcite formation. Moreover, mercury intrusion porosimetry and scanning electron microscopy revealed that the Na2SiO4-activated geopolymer containing 8.5 wt% MgCl2·6H2O exhibited a higher critical pore size (1624 nm) and consequently, a lower 28 d compressive strength (30.1 MPa) and a more loosely bound geopolymer matrix than the salt-free geopolymer. In contrast, MgSO4 addition had less pronounced effects on the setting time, mineral phase, and morphology. The Na2SiO4-activated geopolymer with 9.0 wt% MgSO4 exhibited a compressive strength of 42.8 MPa, also lower than that of the salt-free geopolymer. The results indicate that Cl- is more harmful to the GGBFS-based geopolymer properties and microstructure than SO42- is.
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Breast cancer patients with lymphatic metastasis suffer from poor prognoses. There is an urgent need for controlling lymph node metastasis, but it has proven challenging so far. Here, we implemented LASSO analysis of The Cancer Genome Atlas database to identify genes related to lymph node metastasis and prognosis, and 15 genes were selected. We constructed a functional protein association network and univariate Cox regression to identify significant genes. The results showed that BAHD1 could be predictive of lymph node metastasis as well as prognosis. In vitro studies demonstrated that BAHD1 exerted appreciable effects on the proliferation, migration, and invasion capacity of breast cancer cells. Furthermore, downregulation of BAHD1 induced cell cycle arrest in G1 phase. Additionally, the mRNA levels of CCND1, CDK1 and YWHAZ were decreased upon BAHD1 silencing. These findings indicate that the expression of BAHD1 is essential in the progression of breast cancer, which may provide novel therapeutic and diagnostic clues and insights into the prevention of lymph node metastasis in breast cancer.
Assuntos
Neoplasias da Mama , Neoplasias da Mama/patologia , Proliferação de Células/genética , Proteínas Cromossômicas não Histona , Feminino , Humanos , Metástase Linfática , Prognóstico , RNA Mensageiro/genética , RNA Mensageiro/metabolismoRESUMO
Successful implementation of the sterile insect technique (SIT) against Aedes aegypti and Aedes albopictus relies on maintaining a consistent release of high-quality sterile males. Affordable, rapid, practical quality control tools based on the male's flight ability (ability to escape from a flight device) may contribute to meeting this requirement. Therefore, this study aims to standardize the use of the original FAO/IAEA rapid quality control flight test device (FTD) (version 1.0), while improving handling conditions and reducing the device's overall cost by assessing factors that could impact the subsequent flight ability of Aedes mosquitoes. The new FTD (version 1.1) is easier to use. The most important factors affecting escape rates were found to be tube color (or "shade"), the combined use of a lure and fan, mosquito species, and mosquito age and density (25; 50; 75; 100 males). Other factors measured but found to be less important were the duration of the test (30, 60, 90, 120 min), fan speed (normal 3000 rpm vs. high 6000 rpm), and mosquito strain origin. In addition, a cheaper version of the FTD (version 2.0) that holds eight individual tubes instead of 40 was designed and successfully validated against the new FTD (version 1.1). It was sensitive enough to distinguish between the effects of cold stress and high irradiation dose. Therefore, the eight-tube FTD may be used to assess Aedes' flight ability. This study demonstrated that the new designs (versions 1.1 and 2.0) of the FTD could be used for standard routine quality assessments of Aedes mosquitoes required for an SIT and other male release-based programs.
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Hantavirus infection is a global health challenge, causing widespread public concern. In recent years, cases of hantavirus infection in pregnant women have been reported in many countries. The infected pregnant women and their fetuses appear to have more severe clinical symptoms and worse clinical outcomes. Hence, to study the prevalence of hantavirus infection in pregnant women, this study will focus on the epidemiological distribution of the virus, different virus species penetrating the placental barrier, and factors affecting the incidence and clinical outcome of the infection in pregnant women and their fetuses. In addition, this review will also discuss the diagnostic tools and treatments for pregnant patients and provide an overview of the relevant future research.
Assuntos
Infecções por Hantavirus , Orthohantavírus , Feminino , Humanos , Gravidez , Análise do Polimorfismo de Comprimento de Fragmentos Amplificados , Cesárea , Infecções por Hantavirus/diagnóstico , Infecções por Hantavirus/epidemiologia , Orthohantavírus/genética , PlacentaRESUMO
OBJECTIVE: To investigate the effeicacy of Yishen Huoxue decoction (YSHX) on renal fibrosis induced by unilateral ureteric obstruction (UUO), and on reactive oxygen species (ROS) homeostasis in human umbilical vein endothelial cells (HUVECs). METHODS: Forty male mice were randomly divided into six groups, sham group, UUO group, UUO+ resveratrol (RSV) (15 mg/kg) group, UUO + YSHX 20 mg/kg group (UUO + YSHX-L), UUO + YSHX 40 mg/kg group (UUO + YSHX-M), UUO + YSHX 80 mg/kg group (UUO + YSHX-H). Western blotting was used to measure protein expression levels. Reverse transcription-quantitative polymerase chain reaction was used to measure the mRNA expression. Immunohistochemistry was used to examine the histopathological changes of kidney tissue sample. Cell apoptosis was measured by Annexin V/PI staining. Cell viability was measured using CCK-8/WST-8 assay. RESULTS: YSHX treatment reduced α-SMA and Col-4 expressions, and increased CD31 and VE-cadherin expressions in UUO model mice. In vitro, YSHX increased cell viability and decreased apoptosis of HUVECs under hypoxic conditions. YSHX inhibited ROS generation by activating adenosine monophosphate-activated protein kinase (AMPK)/peroxisome proliferator-activated receptor coactivator-1α (PGC-1α)/silent mating-type information regulation 2 homolog 3 (Sirt3) signaling. CONCLUSION: YSHX treatment reduced 109KJ UUO-induced renal injury and fibrosis. Furthermore, YSHX treatment attenuated hypoxia-induced oxidative stress by regulating AMPK/PGC-1α/Sirt3 signaling.
Assuntos
Sirtuína 3 , Obstrução Ureteral , Monofosfato de Adenosina/metabolismo , Animais , Medicamentos de Ervas Chinesas , Fibrose , Células Endoteliais da Veia Umbilical Humana/metabolismo , Humanos , Hipóxia/metabolismo , Rim/metabolismo , Masculino , Camundongos , Receptores Ativados por Proliferador de Peroxissomo/metabolismo , Proteínas Quinases/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Sirtuína 3/metabolismo , Obstrução Ureteral/tratamento farmacológico , Obstrução Ureteral/genética , Obstrução Ureteral/metabolismoRESUMO
In this study, the seed polysaccharides (PCSP) was ultrasonic-assisted extracted from Pouteria campechiana and optimized by response surface method (RSM). After separation and purification by DEAE-52 cellulose column and Sephadex G-75 glucan gel column, the pure polysaccharide component of PCSPa-1 was obtained, and its structure and antioxidant activity were analyzed. The results showed that the optimal parameters of PCSP with maximum yields (15.94%) were ultrasonic temperature of 79⯰C, ultrasonic time of 69â¯min, and liquid to material ratio of 41â¯mL/g. The molecular weight of PCSPa-1 was 67900â¯Da. PCSPa-1 consisted of glucose and mannose with a molar ratio of 86.65:4.62, and the glycosidic bond mainly included â4)-α-d-Glc(1â and â6)-α-d-Glc(1â. Scanning electron microscopy showed that PCSPa-1 was a strip structure with a smooth surface. In addition, PCSPa-1 had strong scavenging capacity to 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2'-azino-bis- (3-ethylbenzthiaz oline-6-sulphonic acid) (ABTS), hydroxyl radical, and superoxide radical. Polysaccharides of Pouteria campechiana seeds could be exploited as a natural antioxidant.
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Antioxidantes/química , Polissacarídeos/química , Pouteria , Benzotiazóis/química , Compostos de Bifenilo/química , Radical Hidroxila , Picratos/química , Sementes , Ácidos Sulfônicos/química , Superóxidos/químicaRESUMO
An acid-pasting approach is developed in this work to fabricate the composite of perylenetetracarboxylic diimide (PTCDI) and carbon black in concentrated sulfuric acid. Different from traditional mechanical mixing, the solution-based fabrication strategy enables the sufficient blending of PTCDI as active component and carbon black as conductive agent in the PTCDI/CB composite. Serving as the cathode material, the PTCDI/CB composite shows excellent electrochemical performances in both lithium ion battery (137â¯mAhâ¯g-1 at 100â¯mAâ¯g-1 and 110â¯mAhâ¯g-1 at 2000â¯mAâ¯g-1) and sodium ion battery (134â¯mAhâ¯g-1 at 100â¯mAâ¯g-1 and 99â¯mAhâ¯g-1 at 1000â¯mAâ¯g-1), which are comparable to the state-of-art organic/inorganic cathode materials. Considering the simplicity of the processing procedures and the low cost of the starting materials, the acid-pasting approach is a highly attractive method for the solution-based manufacturing of organic secondary battery electrodes.
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A novel method for the determination of Au by inductively coupled plasma mass spectrometry (ICP-MS) is described. Au can be separated and preconcentrated with a micro-column packed with carbon nanofibers as an adsorption material. The adsorption and elution behaviors of Au3+ on carbon nanofibers were systematically investigated under dynamic conditions. The experimental results showed that the studied ions can be adsorbed quantitatively at pH 2.0, and the analytes adsorbed on the column can be eluted with H2NCSNH2-HCl solution at pH 1.0. Under the optimum conditions, the detection limits for Au is 0.15 ng x mL(-1), and the relative standard deviation (RSD) is 8.5% (n = 6). The proposed method has been applied to the determination of trace Au in geological standard material with satisfactory results.
Assuntos
Carbono/química , Ouro/análise , Espectrometria de Massas/métodos , Nanofibras/químicaRESUMO
We herein report an iron-catalyzed direct diazidation method via activation of bench-stable peroxyesters promoted by nitrogen-based ligands. This method is effective for a broad range of olefins and N-heterocycles, including those that are difficult substrates for the existing olefin diamination and diazidation methods. Notably, nearly a stoichiometric amount of oxidant and TMSN3 are sufficient for high-yielding diazidation for most substrates. Preliminary mechanistic studies elucidated the similarities and differences between this method and the benziodoxole-based olefin diazidation method previously developed by us. This method effectively addresses the limitations of the existing olefin diazidation methods. Most notably, previously problematic nonproductive oxidant decomposition can be minimized. Furthermore, X-ray crystallographic studies suggest that an iron-azide-ligand complex can be generated in situ from an iron acetate precatalyst and that it may facilitate peroxyester activation and the rate-determining C-N3 bond formation during diazidation of unstrained olefins.
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Dengue is the most important human arboviral disease in Singapore. We classified residential areas into low-rise and high-rise housing and investigated the influence of urban drainage on the distribution of dengue incidence and outdoor breeding at neighborhood and country scales. In Geylang area (August 2014 to August 2015), dengue incidence was higher in a subarea of low-rise housing compared to high-rise one, averaging 26.7 (standard error, SE = 4.83) versus 2.43 (SE = 0.67) per 1,000 people. Outdoor breeding drains of Aedes aegypti have clustered in the low-rise housing subarea. The pupal density per population was higher in the low-rise blocks versus high-rise ones, 246 (SE = 69.08) and 35.4 (SE = 25.49) per 1,000 people, respectively. The density of urban drainage network in the low-rise blocks is double that in the high-rise ones, averaging 0.05 (SE = 0.0032) versus 0.025 (SE = 0.00245) per meter. Further, a holistic analysis at a country-scale has confirmed the role of urban hydrology in shaping dengue distribution in Singapore. Dengue incidence (2013-2015) is proportional to the fractions of the area (or population) of low-rise housing. The drainage density in low-rise housing is 4 times that corresponding estimate in high-rise areas, 2.59 and 0.68 per meter, respectively. Public housing in agglomerations of high-rise buildings could have a positive impact on dengue if this urban planning comes at the expense of low-rise housing. City planners in endemic regions should consider the density of drainage networks for both the prevention of flooding and the breeding of mosquitoes.