Ion-selective response of visible light photoswitchable indole-hemithioindigo: toward chemical sensing of fluoride and hydroxide.

The chemical sensing of hydrophilic anions such as F- and OH- is of significant importance but also presents considerable challenges. Herein, the thermal E to Z isomerization of a visible-light-responsive photoswitch (HTI-In) is utilized to address this challenge for the first time. The isomerization of HTI-In is dependent on the concentration of F- and OH-, and exhibits excellent selectivity toward F- and OH- over other common anions and cations. Unlike irreversible chemodosimeters and other conventional fluorescent probes, the photodynamic sensing of F- and OH- (demonstrated in solvents and polyurethane hydrogels) is based on a non-equilibrium chemical kinetics and can be operated fully reversibly.

Study on the Common Molecular Mechanism of Metabolic Acidosis and Myocardial Damage Complicated by Neonatal Pneumonia.

Pneumonia is a common clinical disease in the neonatal period and poses a serious risk to infant health. Therefore, the understanding of molecular mechanisms is of great importance for the development of methods for the rapid and accurate identification, classification and staging, and even disease diagnosis and therapy of pneumonia. In this study, a nontargeted metabonomic method was developed and applied for the analysis of serum samples collected from 20 cases in the pneumonia control group (PN) and 20 and 10 cases of pneumonia patients with metabolic acidosis (MA) and myocardial damage (MD), respectively, with the help of ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UPLC-HRMS). The results showed that compared with the pneumonia group, 23 and 21 differential metabolites were identified in pneumonia with two complications. They showed high sensitivity and specificity, with the area under the curve (ROC) of the receiver operating characteristic curve (ROC) larger than 0.7 for each differential molecule. There were 14 metabolites and three metabolic pathways of sphingolipid metabolism, porphyrin and chlorophyll metabolism, and glycerophospholipid metabolism existing in both groups of PN and MA, and PN and MD, all involving significant changes in pathways closely related to amino acid metabolism disorders, abnormal cell apoptosis, and inflammatory responses. These findings of molecular mechanisms should help a lot to fully understand and even treat the complications of pneumonia in infants.

Transformation of CO2 with Glycerol to Glycerol Carbonate over ETS-10 Zeolite-Based Catalyst.

Catalytic conversion of CO2 with the surplus glycerol (GL) produced from biodiesel manufacturing has attracted much academic and industrial attention, which proves the urgent requirement for developing high-performance catalysts to afford significant environmental benefits. Herein, titanosilicate ETS-10 zeolite-based catalysts with active metal species introduced by impregnation were employed for coupling CO2 with GL to efficiently synthesize glycerol carbonate (GC). The catalytic GL conversion at 170 °C miraculously reached 35.0% and a 12.7% yield of GC was obtained on Co/ETS-10 with CH3CN as a dehydrating agent. For comparison, Zn/ETS- Cu/ETS-10, Ni/ETS-10, Zr/ETS-10, Ce/ETS-10, and Fe/ETS-10 were also prepared, which showed inferior coordination between GL conversion and GC selectivity. Comprehensive analysis revealed that the presence of moderate basic sites for CO2 adsorption-activation played a crucial role in regulating catalytic activity. Moreover, the appropriate interaction between cobalt species and ETS-10 zeolite was also of great significance for improving the glycerol activation capacity. A plausible mechanism was proposed for the synthesis of GC from GL and CO2 in the presence of CH3CN solvent over Co/ETS-10 catalyst. Moreover, the recyclability of Co/ETS-10 was also measured and it proved to be recycled at least eight times with less than 3% decline in GL conversion and GC yield after a simple regeneration process through calcination at 450 °C for 5 h in air.

Boosting CO2 hydrogenation to methane over Ni-based ETS-10 zeolite catalyst.

The activation and conversion of the CO2 molecule have always been the most vexing challenge due to its chemical inertness. Developing highly active catalysts, which could overcome dynamic limitations, has emerged as a provable and effective method to promote CO2 activation-conversion. Herein, ETS-10 zeolite-based catalysts, with active nickel species introduced by in situ doping and impregnation, have been employed for CO2 methanation. Conspicuous CO2 conversion (39.7%) and perfect CH4 selectivity (100%) were achieved over the Ni-doped ETS-10 zeolite catalyst at 280°C. Comprehensive analysis, which include X-ray diffraction, N2 adsorption-desorption, SEM, TEM, H2 chemisorption, CO2 temperature programmed desorption, and X-ray photoelectron spectroscopy, was performed. Also, the results indicated that the resultant hierarchical structure, high metal dispersion, and excellent CO2 adsorption-activation capacity of the Ni-doped ETS-10 zeolite catalyst played a dominant role in promoting CO2 conversion and product selectivity.

Perspective on fluorescence cell imaging with ionophore-based ion-selective nano-optodes.

Inorganic ions are ubiquitous in all kinds of cells with highly dynamic spatial and temporal distribution. Taking advantage of different types of fluorescent probes, fluorescence microscopic imaging and quantitative analysis of ion concentrations in cells have rapidly advanced. A family of fluorescent nanoprobes based on ionophores has emerged in recent years with the potential to establish a unique platform for the analysis of common biological ions including Na+, K+, Ca2+, Cl-, and so on. This article aims at providing a retrospect and outlook of ionophore-based ion-selective nanoprobes and the applications in cell imaging.

Investigation of Au/Co3O4 nanocomposites in glycol oxidation by tailoring Co3O4 morphology.

The interfacial perimeter of nanogold and supports is often deemed as the catalytically active site for multiple reactions while the geometrical configuration of the interfacial perimeter at atomic scale is less studied. Herein, gold nanoparticles (NPs) of ca. 2.0 nm are dispersed on Co3O4 support in the shape of nanocubes (dominant Co3O4(001) facet) and nanoplates (Co3O4(111)), which forms different Au-Co3O4 interfaces with respect to the specific facet of the oxide support. A comparison is made on the basis of the interfacial structures and catalytic behavior of ethylene glycol oxidation. STEM analysis identifies that these metallic Au NPs interact with Co3O4 with an orientation relationship of Au/Co3O4(001) and Au/Co3O4(111). XPS and Raman spectroscopy investigations reveal the important variations in the reactivity of surface oxygen, surface Oads/OL ratio, and evolution of surface oxygen vacancies upon variation of the Co3O4 shape. Au/Co3O4-P exhibits much better catalytic activity than the Au/Co3O4-C counterpart in the aerobic oxidation of ethylene glycol, which is promoted by surface oxygen vacancies and intrinsic defects. It has been revealed that the surface oxygen vacancies participate in activating O2, thus making Co3O4-P a superior support for Au NPs in the catalysis of ethylene glycol oxidation.

Underlying mechanisms responsible for restriction of uptake and translocation of heavy metals (metalloids) by selenium via root application in plants.

Since selenium (Se) was shown to be an essential element for humans in 1957, the biofortification of Se to crops via foliar spraying or soil fertilization has been performed for several decades to satisfy the daily nutritional need of humans. Appropriate doses of Se were found to counteract a number of abiotic and biotic stresses, such as exposure to heavy metals (metalloids) (HMs), via influencing the regulation of antioxidant systems, by stimulation of photosynthesis, by repair of damaged cell structures and functions, by regulating the metabolism of some substances and the rebalancing of essential elements in plant tissues. However, few concerns were paid on why and how Se could reduce the uptake of a variety of HMs. This review will mainly address the migration and transformation of HMs regulated by Se in the soil-plant system in order to present a hypothesis of why and how Se can reduce the uptake of HMs in plants. The following aspects will be examined in greater detail, including 1) how the soil characteristics influences the ability of Se to reduce the bioavailability of HMs in soils and their subsequent uptake by plants, which include soil Se speciation, pH, water regime, competing ions and microbes; 2) how the plant root system influenced by Se affects the uptake or the sequestration of HMs, such as root morphology, root iron plaques and root cell wall; 3) how Se combines with HMs and then sequesters them in plant cells; 4) how Se competes with arsenic (As) and thereby reduces As uptake in plants; 5) how Se regulates the expression of genes encoding functions involved in uptake, translocation and sequestration of HMs by Se in plants.

[Combined Effect of Weathered Coal Based Amendments and Soil Water Management on Methylmercury Accumulation in Paddy Soil and Rice Grains].

A pot experiment and field experiment were designed to study the changes in the grain methyl mercury content in paddy soil and rice yield by sowing soil amendments that contained weathered coal, CaCO3, and Na2SeO3 as the main raw materials, combined with water management in a paddy field (80% field capacity after the heading and flowering periods). The results showed that:① In pot experiment, the content of methylmercury in rice rhizosphere soil decreased by 86.6% and the content of methylmercury in the rice grains decreased by 65.2% compared with that of the control. In field experiment, the content of methylmercury in rice rhizosphere soil decreased by 77.4% and the content of methylmercury in rice grains decreased by 60.6% upon adding the amendment+water management compared with that of CK. ② The soil pH increased by more than 0.3 in the pot experiment and 0.2 in the field experiment compared with that of the control. Furthermore, rice yield and plant biomass did not decrease in the two parts of the experiment. It can be inferred that the soil amendment and agronomic regulation measures (water management) used in this study have the advantages of quick effects, convenient use, and remarkable control effects and without secondary pollution. More, they can effectively reduce the risk of rice methylmercury exposure.

Adequate supply of sulfur simultaneously enhances iron uptake and reduces cadmium accumulation in rice grown in hydroponic culture.

Cadmium (Cd) pollution poses serious risks to human health and the rice consumption is a major contribution to dietary intake of this toxic metal. In addition, Cd causes interference to iron (Fe) uptake by rice, leading to Fe deficiency, which is a common malnutrition worldwide. Sulfur (S) is essential for the rice yield and quality; however, the roles of S supply in the Cd and Fe absorption and distribution in rice have not been systematically investigated. Here, we conducted a hydroponic experiment to examine the effects of S application on the uptake and translocation of Cd and Fe in rice under Cd treatment (1.0 µM) combined with four S levels (0, 1.75, 3.5, 7.0 mM). Rice growth was suppressed by Cd but the toxicity was alleviated with S treatment, which also led to decline of Cd concentrations in rice roots, stems and leaves. In the case of low S (1.75 mM), the Fe plaque on the root surface did not decline in the presence of Cd, but it markedly decreased with the increase of S supply (3.5 and 7.0 mM). The Fe contents in rice roots and leaves consistently increased with the S provision regardless of Cd treatment. In addition, the Cd exposure and S supply significantly promoted syntheses of thiol molecules and nicotianamine (NA), but the NA levels in rice tissues decreased when the S addition reached 7.0 mM. Taken together, results of this study demonstrate that sufficient supply of S may augment Fe bioavailability and minimize Cd accumulation in rice under hydroponic conditions.

Efficient synthesis of niobium pentoxide nanowires and application in ethanolysis of furfuryl alcohol.

Nb2O5 nanowires with high specific surface area and crystallinity were prepared by using ammonium oxalate and an acetic acid solvent system. The nanomaterial was applied in ethanolysis of furfuryl alcohol (FA), and the yield of the product, 2-(ethoxymethyl)furan (FEE), achieved was up to 79.6%. Compared to mesoporous Nb2O5 materials and other porous materials, the residence time of FEE on the surface of the catalyst is shorter, and the yield of ethyl levulinate (EL) is lower. Furthermore, a high temperature calcination treatment can change the acid sites and acidity type distribution on the nanowire surface. By XRD, NH3-TPD, IR, and TG-DTA determination methods, it was found that the weak and medium-strong acid sites on the surface of Nb2O5 nanowires were reduced after a 300 °C treatment, and the amount of strong acid was relatively higher. According to the catalytic performance test data and acidity determination, it was concluded that more weak acid and medium-strong acid sites improve the conversion of furfuryl alcohol to FEE, and the strong acid sites promote further conversion of FEE to EL.

Effect of ambient air pollution on premature SGA in Changzhou city, 2013-2016: a retrospective study.

BACKGROUND: Air pollution is becoming an increased burden to the world. Previous studies have confirmed its effects on adverse birth outcomes, but few associated with premature small for gestational age (SGA). We report a retrospective cohort study conducted in Changzhou city to evaluate the association between air pollutants (PM2.5, SO2 and NO2) and premature SGA during pregnancy. METHODS: A total of 46,224 births were collected from January, 2013 to December, 2016, in Changzhou Maternity and Child Health Care Hospital, finally 2709 preterm births were admitted for study. Corresponding air monitoring data were collected from Changzhou Environmental Protection Agency. Generalized estimating equations were used to examine the association between these air pollutants and premature SGA controlling for individual covariates in single- and multi-pollutant models. RESULTS: We found that, in the third trimester, every 10 µg/m3 increments in PM2.5 concentration were associated with premature SGA (OR = 1.18, 95% CI: 1.03-2.83; OR = 1.37, 95% CI: 1.03-3.58) in two- and three-pollutants models. In the whole gestation, a 10 µg/m3 increment in PM2.5 concentration in two- and three-pollutant models were related to premature SGA (OR = 1.53, 95% CI: 1.38-2.47; OR = 1.73, 95% CI: 1.18-2.57). The OR (95% CI) of premature SGA were increasing across quintiles of PM2.5, SO2, NO2 concentrations during the whole gestation period adjusting for confounders (P for trend < 0.001). CONCLUSIONS: These results indicated that pregnant women exposed to PM2.5, combined with other pollutants in the third trimester have a higher risk to deliver premature SGA babies, providing further evidence linking PM2.5 and pregnancy outcomes.

Effect of various chemical oxidation reagents on soil indigenous microbial diversity in remediation of soil contaminated by PAHs.

Chemical oxidation is a promising pretreatment step coupled with bioremediation for removal of polycyclic aromatic hydrocarbons (PAHs). The effectiveness of Fenton, modified Fenton, potassium permanganate and activated persulfate oxidation treatments on the real contaminated soils collected from a coal gas plant (263.6 ±â€¯73.3 mg kg-1 of the Σ16 PAHs) and a coking plant (385.2 ±â€¯39.6 mg kg-1 of the Σ16 PAHs) were evaluated. Microbial analyses showed only a slight impact on indigenous microbial diversity by Fenton treatment, but showed the inhibition of microbial diversity and delayed population recovery by potassium permanganate reagent. After potassium permanganate treatment, the microorganism mainly existed in the soil was Pseudomonas or Pseudomonadaceae. The results showed that total organic carbon (TOC) content in soil was significantly increased by adding modified Fenton reagent (1.4%-2.3%), while decreased by adding potassium permanganate (0.2%-1%), owing to the nonspecific and different oxidative properties of chemical oxidant. The results also demonstrated that the removal efficiency of total PAHs was ordered: permanganate (90.0%-92.4%) > activated persulfate (81.5%-86.54%) > modified Fenton (81.5%-85.4%) > Fenton (54.1%-60.0%). Furthermore, the PAHs removal efficiency was slightly increased on the 7th day after Fenton and modified Fenton treatments, about 14.6%, and 14.4% respectively, and the PAHs removal efficiency only enhanced 4.1% and 1.3% respectively from 1st to 15th day after potassium permanganate and activated persulfate treatments. The oxidants greatly affect the growth of soil indigenous microbes, which cause further influence for PAHs degradation by bioremediation.

Enhanced degradation of polycyclic aromatic hydrocarbons by indigenous microbes combined with chemical oxidation.

In this study, the removal efficiency PAHs by chemical oxidation combined with microbe remediation was evaluated in two contaminated soils. The number of indigenous soil microbes decreased after the addition of chemical oxidants and then increased by nutrients addition. The total removal efficiencies of PAHs by chemical oxidation and nutrient addition followed the order: activated persulfate > potassium permanganate > modified Fenton reagent > Fenton reagent. There are 24.29-27.97%, 22.00-23.67%, 10.24-13.74% and 1.9-2.5% contributions separately due to nutrient treatment in Fenton, modified Fenton, activated persulfate and potassium permanganate treatment, which show significantly difference. The different chemical oxidants exhibited 78-90% removal efficiency for 5-6 rings PAHs, while 52-85% removal efficiency for 2-4 rings PAHs. With the addition of nutrients, the growth of indigenous microbes was enhanced significantly, and the contents of 2-4 rings PAHs in the soil were further decreased. Furthermore, the removal efficiencies of NAP and ANY were increased by more than 45%, while the removal efficiencies of ANE, FLE and PHE were about 30% at Fenton system. There was a complementary enhancing effect of microbial remediation for PAHs degradation after chemical oxidation.

Evaluation of leafy vegetables as bioindicators of gaseous mercury pollution in sewage-irrigated areas.

Mercury (Hg) can evaporate and enter the plants through the stomata of plant leaves, which will cause a serious threat to local food safety and human health. For the risk assessment, this study aimed to investigate the concentration and accumulation of total gaseous mercury (TGM) in five typical leafy vegetables (Chinese chives (Allium tuberosum Rottler), amaranth (Amaranthus mangostanus L.), rape (Brassica campestris L.), lettuce (Lactuca sativa L.), and spinach (Spinacia oleracea L.)) grown on sewage-irrigated areas in Tianjin, China. The following three sites were chosen to biomonitor Hg pollution: a paddy field receiving sewage irrigation (industrial and urban sewage effluents) for the last 30 years, a vegetable field receiving sewage irrigation for 15 years, and a grass field which did not receive sewage irrigation in history. Results showed that the total Hg levels in the paddy (0.65 mg kg-1) and vegetation fields (0.42 mg kg-1) were significantly higher than the local background level (0.073 mg kg-1) and the China national soil environment quality standard for Hg in grade I (0.30 mg kg-1). The TGM levels in ambient air were significantly higher in the paddy (71.3 ng m-3) and vegetable fields (39.2 ng m-3) relative to the control (9.4 ng m-3) and previously reported levels (1.45 ng m-3), indicating severe Hg pollution in the atmospheric environment of the sewage-irrigated areas. Furthermore, gaseous mercury was the dominant form of Hg uptake in the leaves or irreversibly bound to leaves. The comparison of Hg uptake levels among the five vegetables showed that the gradient of Hg accumulation followed the order spinach > red amaranth > Chinese chives > rape > lettuce. These results suggest that gaseous Hg exposure in the sewage-irrigated areas is a dominant Hg uptake route in leafy vegetables and may pose a potential threat to agricultural food safety and human health.

Interactive effects of PAHs with different rings and As on their uptake, transportation, and localization in As hyperaccumulator.

In order to illuminate the mechanism of the interaction of polycyclic aromatic hydrocarbon (PAH) with different benzene rings and arsenic (As) in As hyperaccumulator, Pteris vittata L., the uptakes of PAHs were investigated using hydroponics simulation and localizations of PAHs in the plant were determined using two-photon laser scanning confocal microscopy (TPLSCM). The results showed that the total As concentration in different parts of P. vittata decreased in the presence of PAHs with increased numbers of benzene rings: 38.0-47.4% for benzo(a)pyrene (BaP, five rings), 20.5-35.9% for pyrene (PYR, four rings), and 13.7-16.6% for fluorine (FLU, three rings). BaP and PYR concentrations increased, while FLU concentration decreased in the presence of As. The results of TPLSCM revealed that PAHs distributed in epidermal cells of roots, xylem, and endothelial cells of rachis, epidermis, and stomatal cells of pinnae; however, the fluorescence intensity of BaP and PYR were higher than FLU significantly in plant. This study provided important basis to further research on interactive effects of PAHs and As in the P. vittata. These findings were important to understand the mechanisms of PAH and As translocation and distribution by P. vittata.

Semiautomated Alignment of High-Throughput Metabolite Profiles with Chemometric Tools.

The rapid increase in the use of metabolite profiling/fingerprinting techniques to resolve complicated issues in metabolomics has stimulated demand for data processing techniques, such as alignment, to extract detailed information. In this study, a new and automated method was developed to correct the retention time shift of high-dimensional and high-throughput data sets. Information from the target chromatographic profiles was used to determine the standard profile as a reference for alignment. A novel, piecewise data partition strategy was applied for the determination of the target components in the standard profile as markers for alignment. An automated target search (ATS) method was proposed to find the exact retention times of the selected targets in other profiles for alignment. The linear interpolation technique (LIT) was employed to align the profiles prior to pattern recognition, comprehensive comparison analysis, and other data processing steps. In total, 94 metabolite profiles of ginseng were studied, including the most volatile secondary metabolites. The method used in this article could be an essential step in the extraction of information from high-throughput data acquired in the study of systems biology, metabolomics, and biomarker discovery.

Transportation and localization of phenanthrene and its interaction with different species of arsenic in Pteris vittata L.

The interaction between arsenic (As) and phenanthrene (PHE) in Pteris vittata L. was investigated in this study. The migration and occurrence of PHE in P. vittata were determined by two-photon laser scanning confocal microscopy. Data indicated that PHE supplementation lowers the As concentration in P. vittata, decreasing As levels by 16.8-39.9% in the pinnae, 30.0-49.0% in the rachis, and 45-51.5% in the roots, respectively. Different arsenic species inhibited P. vittata PHE absorption. The most significant effect was observed using dimethylarsenic acid (DMA), which decreased PHE accumulation by 20.73%. With the exception of elevated As(V) concentrations in As(III)-treated plants, PHE treatment significantly reduced inorganic As concentrations in P. vittata. However, PHE elevated root DMA concentrations by 9%. According to in situ visualization, PHE is primarily found in the upper and lower epidermis and stomatal cells, particularly the stomata guard cells.

[Influence of Arsenate and Phenanthrene on Carbon-groups of Pteris vittata L. Roots].

To ascertain absorption of arsenate and phenanthrene as well as their influence on carbon groups in excised roots of Pteris vittata L., the chemical structure of the carbon groups in excised roots was characterized by solid state13C-Nuclear Magnetic Resonance (13C-NMR). The results showed that the excised roots could effectively absorb As and PHE without transpiration, and PHE promoted As accumulation in the roots. Similarly, arsenate increased the adsorption of PHE by the excised roots, the concentration of PHE was increased by 15%-53% compared with CK. The carbon groups of the excised roots were dominated by O-alkyl C, the percentage of carboxyl C was the lowest, mainly composed of carboxylic acids, esters and amides. With the addition of As and PHE, the percentage of carboxyl C increased significantly. The more stable and complex aromatic organic matter was formed to improve the resistance and adaptability in excised roots of Pteris vittata L. under As and PHE stress.

The retention behaviour of amino acids in hydrophilic interaction liquid chromatography on zwitterionic stationary phases.

The retention behaviour of amino acids was studied in hydrophilic LC on zwitterionic stationary phases. Evaluation of the influences of acetonitrile/water content, ammonium acetate (NH4Ac) concentration and mobile phase pH values was performed. Fourteen amino acids were tested and they were all retained to varying extents, with poorer retention in high water content eluents. The linear relationship between the logarithm of retention factor and log(water content) indicated that adsorption dominated or at least was partly involved in the separation mechanism. Electrostatic and hydrophilic interactions also contributed to the retention of these amino acids under different separation conditions with various mobile phase pH values and NH4Ac concentrations. Thus, the overall retention mechanism could be explained as a combination of adsorption, electrostatic and hydrophilic interactions. The magnitude and contribution of each mechanism is dependent on the nature of the analyte and the separation conditions applied.

One- and comprehensive two-dimensional high-performance liquid chromatography analysis of alkylphenol polyethoxylates.

High-performance liquid chromatography (HPLC) analysis of alkylphenol polyethoxylates (APnEOs) in one-dimensional (1-D) mode usually separates either the ethoxy or alkyl moiety distribution and requires different modes for adequate resolution. Simultaneous complete separation of variable ethoxymer chain lengths and variable alkyl end groups using 1-D-HPLC has not been reported and suggests that multidimensional (MDLC) or comprehensive two-dimensional liquid chromatography (LC×LC) might offer a suitable separation approach for this goal. This study compares different separation modes--normal phase LC (NPLC), reversed-phase LC (RPLC) and hydrophilic interaction chromatography (HILIC)--in terms of separation for alkyl and ethoxy distributions. RPLC provided adequate separation of octyl and nonyl APnEOs using an isocratic elution program and was selected as second dimension ((2)D) for LC×LC. NPLC offered better resolution than HILIC; however, non-polar NPLC solvent immiscibility with RPLC mobile phases leads to HILIC being chosen as first dimension ((1)D). The HILIC×RPLC system was evaluated by analysis of four APnEO mixtures. Complete simultaneous separation of APnEOs into individual oligomers, with each alkyl end group resolved, demonstrated the capability of the LC×LC method. Different descriptors and metrics for assessing system orthogonality were investigated to evaluate HILIC×RPLC performance. A relatively high dimensionality of 1.76 was demonstrated.