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Herein, novel MnO2 nanocubes were facilely synthesized by manipulating the dosage of KMnO4 and l-Dopa with the aid of ultrasound. The as-prepared MnO2 nanocubes exhibited interesting oxidation activity which was influenced by the addition order of substrates (H2O2 and 3,3,5,5-tetramethylbenzidine (TMB)). After the mechanism study, we found that H2O2 and TMB can be competitively oxidized by MnO2 nanocubes, which was different from the peroxidase- and oxidase-like activities. According to the discovery, a novel turn-off H2O2 assay method based on MnO2 nanocubes was established, where H2O2 was firstly incubated with MnO2 nanocubes for 3 min and then TMB was added for the instantaneous chromogenic reaction. In addition to the shorter operation time, the colorimetric results were less affected by temperature and unchanged within 30 min without terminating reaction. Moreover, the method showed ultra-high sensitivity with low limit of detection (0.027 µmol L-1) and acceptable reliability for H2O2 assay in water-soak foods.
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Óxidos , Agua , Colorimetría/métodos , Peróxido de Hidrógeno , Límite de Detección , Compuestos de Manganeso , Oxidorreductasas , Reproducibilidad de los Resultados , NanoestructurasRESUMEN
Enzyme mimetics have been widely applied on H2O2 assay, but it is still challenging and interesting to realize the sensitive detection for ultra-trace H2O2. Here, an ultrasensitive Raman assay method based on novel WO3@IP6-Fe3+ enzyme mimetics with peroxidase-like activity was established. WO3 microspheres (MSs) were found to have weak peroxidase-like activity, and the combination of IP6-Fe3+ and WO3 can produce stronger activity. WO3@IP6-Fe3+ MSs showed polyhedron-like structure, uniform size, and smooth surface. Although WO3@IP6-Fe3+ enzyme mimetics have low catalytic efficiency and high absorbance background, the proposed Raman method can bypass the above problems. In Raman method, high concentration of WO3@IP6-Fe3+ can be used to overcome low catalytic efficiency without high absorbance background. Moreover, 3,3',5,5'-tetramethylbenzidine oxide has prominent characteristic Raman peak at 1608 cm-1, greatly improving the sensitivity and eliminating interference of impurities. Due to the high sensitivity and low background, Raman assay showed the ultra-low limit of detection (5.49 × 10-15 M), which was 4-7 orders of magnitude lower than other detection methods. The ultrasensitive Raman assay not only provided the possibility for the enzyme mimetics-based detection of ultra-trace H2O2, but also enable the enzyme mimetics with low activity to be applied.
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Peróxido de Hidrógeno , Peroxidasa , Peróxido de Hidrógeno/química , Peroxidasa/química , Óxidos , Catálisis , Biomimética , Colorimetría/métodosRESUMEN
Annual gross primary productivity (AGPP) is the basis for grain production and terrestrial carbon sequestration. Mapping regional AGPP from site measurements provides methodological support for analysing AGPP spatiotemporal variations thereby ensures regional food security and mitigates climate change. Based on 641 site-year eddy covariance measuring AGPP from China, we built an AGPP mapping scheme based on its formation and selected the optimal mapping way, which was conducted through analysing the predicting performances of divergent mapping tools, variable combinations, and mapping approaches in predicting observed AGPP variations. The reasonability of the selected optimal scheme was confirmed by assessing the consistency between its generating AGPP and previous products in spatiotemporal variations and total amount. Random forest regression tree explained 85 % of observed AGPP variations, outperforming other machine learning algorithms and classical statistical methods. Variable combinations containing climate, soil, and biological factors showed superior performance to other variable combinations. Mapping AGPP through predicting AGPP per leaf area (PAGPP) explained 86 % of AGPP variations, which was superior to other approaches. The optimal scheme was thus using a random forest regression tree, combining climate, soil, and biological variables, and predicting PAGPP. The optimal scheme generating AGPP of Chinese terrestrial ecosystems decreased from southeast to northwest, which was highly consistent with previous products. The interannual trend and interannual variation of our generating AGPP showed a decreasing trend from east to west and from southeast to northwest, respectively, which was consistent with data-oriented products. The mean total amount of generated AGPP was 7.03 ± 0.45 PgC yr-1 falling into the range of previous works. Considering the consistency between the generated AGPP and previous products, our optimal mapping way was suitable for mapping AGPP from site measurements. Our results provided a methodological support for mapping regional AGPP and other fluxes.
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Cambio Climático , Ecosistema , Secuestro de Carbono , Suelo , Aprendizaje Automático , Carbono , Dióxido de Carbono/análisisRESUMEN
Quinoa is an excellent source of γ-aminobutyric acid (GABA), which is a natural four-carbon non-protein amino acid with great health benefits. In this study, the quinoa was treated by cold stress before fermentation with Lactobacillus plantarum to enhance the amount of GABA. The best Lactobacillus plantarum for GABA production was selected from sixteen different strains based on the levels of GABA production and the activity of glutamic acid decarboxylase (GAD). Cold stress treatments at 4 °C and at -20 °C enhanced the amount of GABA in the fermented quinoa by a maximum of 1191% and 774%, respectively. The surface of the fermented quinoa flour treated by cold stress showed more pinholes, mucus, faults and cracks. A Fourier transform infrared spectrophotometer (FTIR) analysis revealed that cold stress had a violent breakage effect on the -OH bonds in quinoa and delayed the destruction of protein during fermentation. In addition, the results from the rapid visco analyzer (RVA) showed that the cold stress reduced the peak viscosity of quinoa flour. Overall, the cold stress treatment is a promising method for making fermented quinoa a functional food by enhancing the production of bioactive ingredients.
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A colorimetric assay based on an enzyme-inhibition strategy is promising for the on-site detection of pesticide residues. Due to the high cost and low stability of enzymes, nanozymes (nanomaterials with enzyme-like activities) are widely developed as substitutes of enzymes. However, the inhibition of pesticides toward enzymes and nanozymes generally lacks selectivity. It is of great significance and challenge to design a specific pesticide assay based on an activity-inhibition strategy. Here, we discovered that iridium nanoparticles possess both peroxidase-like and oxidase-like activities under the same conditions, and their catalytic mechanisms are different. The synergistic effect of dual enzyme-like activities enhanced the colorimetric signal. Interestingly, the dual enzyme-mimicking activities could be simultaneously inhibited, and the inhibition effect exhibited high selectivity toward malathion. Considering the popularity and the hazards of malathion, a malathion assay method based on activity inhibition was established without enzymes and a redundant process. The synergistic effect of the selective inhibition of dual enzyme-like activities enhanced the selectivity and sensitivity. The proposed assay strategy opens up an avenue for specific assay of various pesticides.
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Colorimetría , Nanoestructuras , Catálisis , Colorimetría/métodos , Iridio , Malatión/farmacologíaRESUMEN
Considering DNA-based homogeneous electrochemical assay allows identification of targets to be carried out in a homogeneous solution, it would be of significance to develop the successive homogeneous assay system in dynamic solution for rapid disease diagnosis and high-throughput bioanalysis. In homogeneous assay, the work electrodes generally have capability of DNA capture but lack signal amplification, restricting its sensitivity. Here, a flow-homogeneous sensing system was proposed to realize the successive assay of microRNA, a model biomarker. Ultrathin 2D metal-organic framework (MOF) nanozymes with thickness of about 1 nm were facilely prepared by ultrasonic approach. Due to the excellent enzyme-like activity and adsorption capacity towards single-strand DNA (ssDNA), MOF nanozymes adsorbed on electrode simultaneously played two roles of ssDNA collector and signal-amplifier. To adapt the recoverable electrode to on-line monitoring, duplex-specific nuclease-assisted circle reaction was conducted to produce the turn-on amplified signal. Flow injection device was employed to realize the recycling of electrodes and the successive microRNA assay. The assay strategy showed low limit of detection (0.12 pM, S/N = 3) for microRNA, excellent renewability and acceptable reliability for real sample assay. The established system exerts the advantages of DNA-based homogeneous electrochemical sensing strategy. This work would not only expand homogeneous electrochemical assay to successive bioassay, but also provide the possibility for practical application of homogeneous sensing strategy.
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Técnicas Biosensibles , Estructuras Metalorgánicas , MicroARNs , ADN , Técnicas Electroquímicas , Límite de Detección , MicroARNs/análisis , Reproducibilidad de los ResultadosRESUMEN
Clarifying the relationship between meteorological factors and ozone can provide scientific support for ozone pollution prediction, but the effects of boundary layer meteorology, especially boundary layer height and turbulence, on ozone pollution are rarely studied. Here, ozone and its related meteorological factors were observed in summer in Shijiazhuang, a city with the most serious ozone pollution on the North China Plain. The forced and free convection boundary layers were classified using ground remote observations. After eliminating the forced convection condition, strong free convection conditions, exhibiting a high boundary layer height, high wind speed, strong turbulence and large-scale free convection velocity, were found to be beneficial for the aggravation of ozone pollution. Combined with the ozone profile detected by a tethered balloon, the ozone chemical budget was calculated using the differences in the column ozone concentrations between the morning and afternoon, and the results confirmed the impact of free convection intensity on ozone pollution. The change in ozone sensitivity from VOCs sensitivity to NOx sensitivity driven by strong free convection was the main reason for the deterioration of ozone pollution. This study clarified the impact of boundary layer meteorology on ozone and its sensitivity and has important practical significance for ozone pollution prevention and early warning.
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Monitoring vegetation change and their potential drivers are important to environmental management. Previous studies on vegetation change detection and driver discrimination were two independent fields. Specifically, change detection methods focus on nonlinear and linear change behaviors, i.e., abrupt change (AC) and gradual change (GC). But driver discrimination studies mainly used linear coupling models which rarely concerned the nonlinear behaviors of vegetation. The two diagnoses need be treated as sequential flow because they have inner causality mechanisms. Furthermore, ACs concealed in time series may induce over/under-estimate contributions from human. We chose the Yangtze River Basin of China (YRB) as a study area, first separated ACs from GCs using breaks for additive and seasonal trend method, then discriminated drivers of GCs using optimized Restrend method. Results showed that (1) 2.83% of YRB were ACs with hotspots in 1998 (30.2%), 2003 (10.4%), and 2002 (7.6%); 66.7% of YRB experienced GC with 94.8% of which were positive; and (2) climate induced more area but less dramatic GCs than human activities. Further analysis showed that temperature was the main climate driver to GCs, while human-induced GCs were related to local eco-policies. The widely occurring ACs in 1998 were related to the flooding catastrophe, while the dramatic ACs in sub-basin 12 in 2003 may result from urbanization. This paper provides clear insights on the vegetation changes and their drivers at a relatively long perspective (i.e., 34 years). Sequential combination of specifying different vegetation behaviors with driver analysis could improve driver characterizations, which is key to environmental assessment and management in YRB.
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Cambio Climático , Ríos , China , Clima , Monitoreo del Ambiente , HumanosRESUMEN
BACKGROUND: Emerging studies have reported that long non-coding RNAs (lncRNAs) were crucial regulators in the progression of colorectal cancer (CRC). LncRNA susceptibility 9 (CASC9) was involved in several cancers; however, its role in CRC remains unknown. METHODS: RT-PCR was done to probe the expression of CASC9 and miR-193a-5p in CRC samples. CRC cell lines (HCT116 and SW480) were used as cell models. The biological influence of CASC9 on cancer cells was studied using CCK-8 assay, Transwell assay and TUNEL assay in vitro, and subcutaneous xenotransplanted tumor model in vivo. Interaction between CASC9 and miR-193a-5p was investigated by bioinformatics analysis, RT-PCR, and luciferase reporter assay. The expression level of the downstream gene of miR-193a-5p, erb-b2 receptor tyrosine kinase 2 (ERBB2), was tested by Western blot. RESULTS: CASC9 was significantly up-regulated in CRC samples, while miR-193a-5p was markedly down-regulated. Overexpression of CASC9 promoted viability, migration and invasion of CRC cells, while overexpression of miR-193a-5p had the opposite effect. CASC9 could down-regulate miR-193a-5p via sponging it, and there was a negative relevancy between CASC9 and miR-193a-5p in CRC samples. CASC9 also enhanced the expression levels of ERBB2, while this effect could be reversed by co-transfection with miR-193a-5p. CONCLUSION: CASC9, an oncogenic lncRNA, was abnormally up-regulated in CRC tissues, and it could indirectly modulate the expression of ERBB2 via reducing the expression level of miR-193a-5p.
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The North China Plain (NCP) is a major grain production zone that plays a critical role in ensuring China's food supply. Irrigation is commonly used during grain production; however, the high annual water deficit [precipitation (P) minus evapotranspiration (ET)] in typical irrigated cropland does not support double cropping systems (such as maize and wheat) and this has resulted in the steep decline in the water table (~0.8 m year-1 at the Luancheng station) that has taken place since the 1970s. The current study aimed to adapt and check the ability of the CropSyst model (Suite-4) to simulate actual evapotranspiration (ETa), biomass, and grain yield, and to identify major evaporation (E) losses from winter wheat (WW) and summer maize (SM) rotations. Field experiments were conducted at the Luancheng Agro-ecosystem station, NCP, in 2010-2011 to 2012-2013. The CropSyst model was calibrated on wheat/maize (from weekly leaf area/biomass data available for 2012-2013) and validated onto measured ETa, biomass, and grain yield at the experimental station from 2010-2011 to 2011-2012, by using model calibration parameters. The revalidation was performed with the ETa, biomass, grain yield, and simulated ETa partition for 2008-2009 WW [ETa partition was measured by the Micro-lysimeter (MLM) and isotopes approach available for this year]. For the WW crop, E was 30% of total ETa; but from 2010-11 to 2013, the annual average E was ~40% of ETa for the WW and SM rotation. Furthermore, the WW and SM rotation from 2010-2011 to 2012-2013 was divided into three growth periods; (i) pre-sowing irrigation (PSI; sowing at field capacity) to emergence period (EP), (ii) EP to canopy cover period (CC) and (iii) CC to harvesting period (HP), and E from each growth period was ~10, 60, and 30%, respectively. In general, error statistics such as RMSE, Willmott's d, and NRMSE in the model evaluation for wheat ETa (maize ETa) were 38.3 mm, 0.81, and 9.24% (31.74 mm, 0.73, and 11.89%); for wheat biomass (maize biomass) they were 1.25 Mg ha-1, 0.83, and 9.64% (0.78 Mg ha-1, 0.96, and 7.96%); and for wheat grain yield (maize grain yield) they were 0.65 Mg ha-1, 0.82, and 9.87% (0.2 Mg ha-1, 0.99, and 3.79%). The results showed that CropSyst is a valid model that can be use with a reliable degree of accuracy for optimizing WW and SM grain yield production and water requirement on the NCP.