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The uptake, translocation, and transformation of engineered nanoparticles (ENPs) in plants present significant challenges due to the lack of effective determination methods. This is especially true for selenium nanoparticles (SeNPs), which hold promise for Se-biofortified agriculture and exhibit dynamic behaviors within plant system. Herein, we proposed a novel approach that incorporates enzymic digestion and membrane filtration to selectively extract SeNPs and dissolved Se from plant tissues, employing rice (Oryza sativa) plant as a model. Subsequently, the SeNPs retained on the membrane were quantified using inductively coupled plasma mass spectrometry (ICPMS), while the dissolved Se in the filtrate, including selenite (Se(IV)), selenate (Se(VI)), and seleno amino acid, were analyzed by liquid chromatography coupled with ICPMS (LC-ICPMS). Recoveries of 83.5–91.4% for SeNPs and 73.6–99.4% for dissolved Se at a spiking level of 8 μg/g in quality control samples were obtained. With the established method, it was discovered that SeNPs taken up by rice leaves can transform into Se (IV) and organic Se, and all the Se species could be translocated downward, but only Se (IV) and SeNPs could be excreted through the roots. These findings provide valuable insights into the fate of SeNPs in plants and their related biological responses.

Biochar has demonstrated significant promise in addressing heavy metal contamination and methane (CH4) emissions in paddy soils; however, achieving a synergy between these two goals is challenging due to various variables, including the characteristics of biochar and soil properties that influence biochar’s performance. Here, we successfully developed an interpretable multitask deep learning (MTDL) model by employing a tensor tracking paradigm to facilitate parameter sharing between two separate data sets, enabling a synergy between Cd and CH4mitigation with biochar amendments. The characteristics of biochar contribute similar weightings of 67.9% and 62.5% to Cd and CH4mitigation, respectively, but their relative importance in determining biochar’s performance varies significantly. Notably, this MTDL model excels in custom-tailoring biochar to synergistically mitigate Cd and CH4in paddy soils across a wide geographic range, surpassing traditional machine learning models. Our findings deepen our understanding of the interactive effects of Cd and CH4mitigation with biochar amendments in paddy soils, and they also potentially extend the application of artificial intelligence in sustainable environmental remediation, especially when dealing with multiple objectives.

Anions accompanying inorganic fertilizers, such as chloride and sulfate ions, potentially affect the solubility, uptake, and transport of Cd to rice grains. However, the role of anions in controlling Cd transport in the soil–soil solution–Fe plaque–rice plant continuum remains poorly understood. Cd isotope ratios were applied to Cd-contaminated soil pots, hydroponic rice, and adsorption experiments with or without KCl and K2SO4treatments to decipher transport processes in the complex soil–rice system. The chloride and sulfate ions increased the Cd concentrations in the soil solution, Fe plaque, and rice plants. Accordingly, the magnitude of positive fractionation from soil to the soil solution was less pronounced, but that between soil and Fe plaque or rice plant is barely varied. The similar isotope composition of Fe plaque and soil, and the similar fractionation magnitude between Fe plaque and the solution and between goethite and the solution, suggested that desorption-sorption between iron oxides and the solution could be important at the soil–soil solution–Fe plaque continuum. This study reveals the roles of chloride and sulfate ions: (i) induce the mobility of light Cd isotopes from soil to the soil solution, (ii) chloro-Cd and sulfato-Cd complexes contribute to Cd immobilization in the Fe plaque and uptake into roots, and (iii) facilitate second leaves/node II-to-grain Cd transport within shoots. These results provide insights into the anion-induced Cd isotope effect in the soil–rice system and the roles of anions in facilitating Cd migration and transformation.

Chemical oxidation of As(III) by iron (Fe) oxyhydroxides has been proposed to occur under anoxic conditions and may play an important role in stabilization and detoxification of As in subsurface environments. However, this reaction remains controversial due to lack of direct evidence and poorly understood mechanisms. In this study, we show that As(III) oxidation can be facilitated by Fe oxyhydroxides (i.e., goethite) under anoxic conditions coupled with the reduction of structural Fe(III). An excellent electron balance between As(V) production and Fe(III) reduction is obtained. The formation of an active metastable Fe(III) phase at the defective surface of goethite due to atom exchange is responsible for the oxidation of As(III). Furthermore, the presence of defects (i.e., Fe vacancies) in goethite can noticeably enhance the electron transfer (ET) and atom exchange between the surface-bound Fe(II) and the structural Fe(III) resulting in a two time increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites is likely to facilitate As(III) coordination and ET with structural Fe(III) based on electrochemical analysis and theoretical calculations showing that this reaction pathway is thermodynamically and kinetically favorable. Our findings highlight the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation, shedding a new light on As risk management in soils and subsurface environments.

A nickel-based catalytic system, including simple NiCl2·6H2O, sodium borohydride and mercapto-β-cyclodextrin (CD-SH), is developed for the semi-hydrogenation of alkynes to E-alkenes. This system features a high efficiency with good E-selectivity at room temperature. The high efficiency is not only due to the highly active Hδ−(NaBH4), Hδ+(methanol) and in situformed Ni nanoparticles, but also because of the host–guest interaction between CD-SH and Z-alkene intermediate. Kinetic and mechanistic studies demonstrate that the E-alkene is obtained viaan efficient Z-selective semi-hydrogenation, followed by a sulfur-radical mediated Z-to-Eisomerization. This study provides a cheaper, efficient and practical strategy for the activity and selectivity improvement of E-selective semi-hydrogenation of alkynes.

• A nonlinear discrete grey model is developed to assess the intervention effect. • A new intervention effect-based nonlinear discrete grey forecasting model is designed. • Effect of a carbon emissions trading scheme on emissions intensity is assessed. • The novel model can predict carbon emissions intensity under policy intervention. • Empirical results demonstrate the novel model's excellent forecasting performance. In the context of severe global warming, accurately exploring the trend of carbon emissions intensity (CEI) changes is of great significance for mitigating climate change issues. The implementation of China's Carbon Emissions Trading Scheme (ETS) in 2013 is a policy intervention aimed at influencing CEI. The impact of intervention events makes forecasting a complex problem, which poses significant challenges to the construction of forecasting models. We first develop a quadratic time-varying nonlinear discrete grey model (QDNDGM(1,1)) to assess the intervention effect of the ETS policy. Then, a novel intervention effect-based quadratic time-varying nonlinear discrete grey model (IE-QDNDGM(1,1)) is developed to conduct the prediction under intervention effect, including an intervention term. The Whale Optimization Algorithm (WOA) is used to calculate a nonlinear parameter. We assess the intervention effect of the ETS policy in China and find that it can indeed reduce CEI. We verify the IE-QDNDGM(1,1) model's superiority by comparing its predictive performance with that of three grey models, one statistical technique, and one artificial intelligence model. The comparative study shows the proposed model's excellent fitting and prediction performance. An ablation experiment is conducted to validate the design of the IE-QDNDGM(1,1) model. Policy implications of the ETS intervention effect are discussed. [ABSTRACT FROM AUTHOR]

Elimination or blocking of astrocytes could ameliorate neuropathic pain in animal models. MiR-125a-5p, expressed in astrocyte derived extracellular vesicles, could mediate astrocyte function to regulate neuron communication. However, the role of miR-125a-5p in DPN (diabetic peripheral neuropathy) remains elusive.

Agricultural land degradation is posing a serious threat to global food security. Restoration of the degraded land has traditionally been viewed as an inherently sustainable practice; however, restoration processes render consequential environmental impacts which could potentially exceed the benefit of restoration itself. In the present study, an integrated life cycle assessment analysis was conducted to evaluate life cycle primary, secondary, and tertiary impacts associated with the restoration of the contaminated agricultural land. The results demonstrated the importance of including spatially differentiated impacts associated with managing the land and growing crops. Comparing four risk management scenarios at a contaminated field in Southern China, it was found that the primary and secondary impacts followed the order of no action > chemical stabilization > phytoextraction > alternative planting. However, when tertiary impacts were taken into account, alternative planting rendered much higher footprint in comparison with phytoextraction and chemical stabilization, which provides evidence against an emerging notion held by some policy makers. Furthermore, assuming that the loss of the rice paddy field in Southern China is compensated by the deforested land in the Amazon rainforest, the total global environmental impact would far exceed that of no action, resulting in 687 ton CO2-e ha–1of climate change impact. Overall, the present study provides new research findings to support more holistic policy making and also sheds lights on the future development of various restoration technologies.

A facile strategy for the free radical polymerization and coupling of −OH groups and −NCO groups in one pot was carried out to synthesize hyperbranched poly(6-O-methacryloyl mannose/2-isocyanatoethyl methacrylate)s [HGP(MaM-co-IM)s]. The effects of the reaction conditions on the molecular parameters of HGP(MaM-co-IM)s were investigated in detail. The key molecular parameter, degree of branching (DB), was estimated from the content of elemental nitrogen that existed solely in the branching units. The DB values and molecular weights of HGP(MaM-co-IM)s can be tuned by the feed ratio of MaM/IM and the reaction time, respectively. Moreover, a mechanism for this one-pot method was proposed with the assistance of 1H nuclear magnetic resonance (NMR), 13C NMR, multidetector size exclusion chromatography, elemental analysis, and Fourier transform infrared spectroscopy. In addition, the performance parameters of HGP(MaM-co-IM)s, including loading capacity, biodegradability, and ability to inhibit hen egg white lysozyme fibrillation, were also studied, and the results suggested that HGP(MaM-co-IM)s will have broad applications in the biochemical field.

Nanoscale zero-valent bimetals are receiving considerable attention because of their excellent capability to degrade organic pollutants in water; however, nanoparticle aggregation reduces their reactivity, and the difficult separation limits their general application. Herein, we have developed a novel graphene aerogel anchored nano zero-valent iron and copper (GA-Fe/Cu) composite for the removal of 2,4-dichlorophenol (DCP) through activation by persulfate (PS) under aerobic conditions. The results show that the GA-Fe/Cu aerogel exhibits outstanding performances in the DCP degradation by PS activation, which increase as the Fe/Cu loading increases from 3.1% [GA-Fe/Cu(3.1)] to 9.4% [GA-Fe/Cu(9.4)]. The GA-Fe/Cu(9.4) aerogel exhibits an optimal catalytic activity for DCP degradation (∼100%) by PS activation within 60 min (k1= 0.0748 min−1). The degradation efficiency of DCP by GA-Fe/Cu(9.4) significantly increases with increasing PS concentration, and slightly decreases from 100% to 80% upon increasing the pH from 4.5 to 9.5. The SO4−, OH, and O2−radicals are found to be the dominant reactive oxygen species (ROS) generated by PS activation with GA-Fe/Cu(9.4), while non-radical mechanisms induced by GA appear to be also responsible for the DCP degradation. In addition, 83.2% of DCP is found to be completely mineralized by this reaction system. Thus, the findings of this work provide an alternative route for the efficient removal of organic pollutants from water.

An efficient methodology has been developed to determine the tricyclazole residue in matrix based on surface-enhanced Raman scattering (SERS) coupled with dispersible matrix solid-phase extraction. After pretreatment and test conditions optimization, peaks at 1373 and 1317 cm–1in the SERS spectrum were respectively selected as quantitative peaks for rice and Brassica campestrisL. ssp. chinensisvar. utilisTsen, respectively. The matrix standard curve-external standard method was used to quantitatively conduct a statistical analysis. The correlation between the quantitative peak response and tricyclazole concentration showed a significant linear relationship with a correlation coefficient of R2> 0.99. The lowest spiked concentration was determined to be the quantitative limit that was below the maximum residue limits of tricyclazole. This study provides a sensitive, stable and rapid approach for the analysis of tricyclazole in above matrix viaSERS, and it will be a useful complement to the quantitative analysis of tricyclazole in a complex matrix.

While it was recently reported that the conduction band of iron minerals can mediate electron transfer between Fe(II) and different Fe(III) lattice sites during Fe(II)-catalyzed mineral transformation, it is unclear whether such a conduction band mediation pathway occurs in the microbial Fe(II) oxidation system under dark and anoxic subsurface conditions. Here, using cytochrome c(c-Cyts) as a model protein of microbial Fe(II) oxidation, the in vitrokinetics and thermodynamics of c-Cyts reduction by Fe(II) were studied. The results showed that the rates of c-Cyts reduction were greatly enhanced in the presence of the semiconducting mineral hematite (Hem, α-Fe2O3). The electrochemical experiments separating Fe(II) and c-Cyts demonstrated that electrons from Fe(II) to the electrode or from the electrode to c-Cyts could directly penetrate hematite, resulting in enhanced current. Independent photochemical and photoluminescence experiments indicated that c-Cyts could be directly reduced by the conduction band electrons of hematite which were generated under light illumination. In c-Cyts+Fe(II)+Hem, the redox potential of Fe(II)-Hem was shifted from −0.15 to −0.18 V and that of c-Cyts+Hem changed slightly from −0.05 to −0.04 V. For the bulk hematite, Mott–Schottky plots illustrated that the flat band was shifted negatively and positively in the presence of Fe(II) and oxidized c-Cyts, respectively, and the surface electron/charge density was higher in the presence of Fe(II)/c-Cyts. As a consequence, the redox gradients from adsorbed Fe(II) to adsorbed c-Cyts allow electron transfer across the conduction band of hematite and facilitate c-Cyts reduction. This mechanistic study on conduction band-mediating electron transfer could help interpret the role of semiconducting minerals in the microbial Fe(II) oxidation process under dark anoxic conditions.

ABSTRACTTo capture decision-makers' (DMs') various kinds of misperceptions in a conflict setting, a methodology is developed to improve hypergame analysis within the framework of the graph model for conflict resolution. This technique models and analyses DMs' different levels of perception in a real-life situation. It also handles a DM's misperception about itself as well as misperception about its opponents. A hypergame in graph form is a framework that consists of subjective hypergames, each of which illustrates a given DM's viewpoint of the hypergame situation. The universal sets of options and states for the hypergame, which include all possible perceptual options and states for the conflict, are used to construct each DM's subjective hypergame. To gain worthy strategic insights from the hypergame analysis, the overall hypergame equilibria are classified based on the types of misperceptions and the awareness of DMs into eight classes of resolutions.

The effect of Zn on Cd accumulation in rice varies under flooding and drainage conditions, and the underlying mechanism during uptake and transport from the soil to grains remains unclear. Isotope fractionation and gene expression were investigated using pot experiments under distinct water regimes and with Zn addition to gain a deeper understanding of the molecular effects of Zn on Cd uptake and transport in rice. The higher OsHMA2expression but constitutively lower expression of zinc-regulated, iron-regulated transporter-like protein (ZIP) family genes in roots under the drainage regime than the flooding regime caused the enrichment of nonheavy Zn isotopes in the shoots relative to roots but minimally affected Cd isotopic fractionation. Drainage regime seem to exert a striking effect on the root-to-shoot translocation of Zn rather than Cd, and increased Zn transport via OsHMA2. The changes in expression patterns in response to Zn addition were similar to those observed upon switching from the flooding to drainage regime, except for OsNRAMP1and OsNRAMP5. However, soil solution-to-rice plants and root-to-shoot fractionation toward light Zn isotopes with Zn addition (Δ66Znrice plant-soil solution= −0.49 to −0.40‰, Δ66Znshoot-root= −0.36 to −0.27‰) indicated that Zn transport occurred via nonspecific uptake pathways and OsHMA2, respectively. Accordingly, the less pronounced and minimally varied Cd isotope fractionation suggested that OsNRAMP5 and OsHMA2 are crucial for Cd uptake and root-to-shoot transport, respectively, facilitating Cd accumulation in grains. This study demonstrated that a high Zn supply promotes Cd uptake and root-to-shoot transport in rice by sharing distinct pathways, and by utilizing a non-Zn-sensitive pathway with a high affinity for Cd.

Green rusts (GRs) interlayered with Cl−, SO42−, and CO32−were used to reduce tetrabromobisphenol A (TBBPA), which is the most widely used brominated flame retardant. The modification of GRs by copper nanoparticles (Cu NPs) greatly enhanced the reductive reactivity of GR. GR(Cl)–Cu NPs with a Cu NPs content of 0.5% had the highest reactivity toward TBBPA reduction. High pH did not favor TBBPA reduction by both GR(Cl) and GR(Cl)–Cu NPs. The presence of SO42−and CO32−inhibited TBBPA reduction by GR(Cl) and GR(Cl)–Cu NPs, whereas the inhibition effect of PO43−and humic acid was much greater than those for SO42−and CO32−. The TBBPA reduction by GR(Cl)–Cu NPs could be explained by a galvanic cell model, where electrons are transferred from GR(Cl) to Cu NPs, where TBBPA reduction occurs. Our findings demonstrate that nature-occurring Fe-bearing minerals may play an important role in the reductive transformation of TBBPA besides the biotransformation and that GR(Cl)–Cu NPs can be used for the efficient removal of reducible halogenated pollutants.

The effectiveness of ClO2bleaching as a replacement for conventional Cl2bleaching, which is intensively practiced in developing countries, to reduce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in non-wood pulp and paper mills has not been field tested. The first field study was performed to investigate PCDD/F variations when ClO2bleaching was used as a substitute for conventional Cl2bleaching in a non-wood pulp and paper mill. It was found that the PCDD/F toxic equivalents (TEQs) in solid and effluent samples were approximately 1.3–14.9 times lower when ClO2bleaching was used instead of the conventional Cl2bleaching. 2,3,7,8-Substituted tetrachlorinated dibenzofurans (2,3,7,8-TCDF) were the dominant contributors to total PCDD/F TEQs in samples from the investigated mill when using conventional Cl2bleaching. The formation amounts of 2,3,7,8-TCDF were reduced from 1.56–2.76 pg TEQ/g to 0.02–0.32 pg TEQ/g in solid samples when ClO2bleaching was used instead of the conventional Cl2bleaching. The replacement of Cl2with ClO2might decrease the chlorination reactions of dibenzofuran as potential precursors, and thus reduce the formation amounts of 2,3,7,8-TCDF. The results could provide important knowledge for suggesting the best available technique for PCDD/F reduction for non-wood pulp and paper mills in developing countries.

A smooth and flat uranium surface with trace of well-defined grain boundaries has been obtained by electropolishing in the Lewis acidic AlCl3-1-ethyl-3-methylimidazolium chloride ionic liquid. The surface roughness Ra and Ry of the uranium reduced substantially from 130.1 nm and 899.4 nm to 16.77 nm and 206.89 nm after electropolishing, respectively. The underlying mechanism of electropolishing has been investigated by the combination of electrochemical, spectroscopic and surface characterization methods. A current density plateau in the measured polarization curves of uranium is observed, which is directly related to the mass transport limit of U3+. The mass transport mechanism of the process follows the salt precipitation model, and the precipitate is proposed to be in the form of U(Al2Cl7)x(AlCl4)3-x.

The positive impacts of managing projects as a portfolio are quantified by comparing the value of the integrated risk of a project portfolio and the aggregation of single project risks implemented separately. Firstly, the integrated risk is defined by proposing risky events based on set theory. Secondly, as projects interact with each other in a project portfolio, the integrated risk is evaluated by using a Bayesian network structure learning algorithm to construct an interdependent network of risks. Finally, the integrated risk of a practical case is assessed using this method, and the results show that the proposed method is an effective tool for calculating the extent of risk reduction of implementing a project portfolio and identifying the most risky project, so as to assist companies in making comprehensive decisions in the phase of portfolio selection and portfolio controlling.

A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for simultaneous determination of two hydrophilic aminoglycosides, kasugamycin and validamycin-A, in a variety of matrices (apples, cabbage, cucumbers, lettuce, tomatoes, and eggplant) has been developed. The proposed method provides sufficient sensitivity and excellent chromatographic performance using a special ReproSil 100 C18column with 0.1% formic acid as the mobile phase additive. Accurate mass information for both analytes was obtained based on time-of-flight (TOF) mass spectrometry. The methanol/water (70 : 30, v/v) with pH adjusted to 5.5 was selected as the extraction solvent. The combination of hydrophilic–hydrophobic-balanced (HLB) cartridges with strong cation exchange SCX cartridges was used to purify the extracts with strongly polar compounds and satisfactory results were obtained. The consecutive solid-phase extraction minimized signal suppression/enhancement which led to matrix effects in the range of −12.6 to 6.11% only. Recovery experiments were performed for both compounds at three levels (50, 100, and 500 μg kg−1) in six different matrices and yielded good recoveries ranging from 81.7% to 108% with relative standard deviation values below 13%. The limits of quantification (LOQs) for kasugamycin and validamycin-A were 4.1 μg kg−1and 1.0 μg kg−1, respectively.

The bioavailability of arsenic (As) is influenced by ammonium (NH4+-N) fertilization, but the underlying mechanisms controlling As transformation in soil-rice systems are still not fully understood. The effects of two NH4+-N fertilizers, urea and NH4HCO3, on the transformation of As in a paddy soil with low organic matter content and transfer in rice plants were investigated. Treatments with urea and NH4HCO3significantly increased arsenite (As(III)) concentration in porewater, bioavailable As in rhizosphere soil, and the relative abundance of the As(V) respiratory reductase gene (arrA) and As(III) methyltransferase gene (arsM). Furthermore, the relative expression of As transporter genes in rice roots, such as OsLsi1, OsLsi2, and OsLsi3, was upregulated, and the translocation efficiency of As(III) from rice roots to brown rice was promoted. Subsequently, As(III) accumulation in brown rice significantly increased. Therefore, attention should be paid to As-contaminated paddy fields with NH4+-N fertilization.

The dark production of reactive oxygen species (ROS) coupled to biogeochemical cycling of iron (Fe) plays a pivotal role in controlling arsenic transformation and detoxification. However, the effect of secondary atom incorporation into Fe(III) oxyhydroxides on this process is poorly understood. Here, we show that the presence of oxygen vacancy (OV) as a result of Cu incorporation in goethite substantially enhances the As(III) oxidation by Fe(II) under oxic conditions. Electrochemical and density functional theory (DFT) evidence reveals that the electron transfer (ET) rate constant is enhanced from 0.023 to 0.197 s–1, improving the electron efficiency of the surface-bound Fe(II) on OV defective surfaces. The cascade charge transfer from the surface-bound Fe(II) to O2mediated by Fe(III) oxyhydroxides leads to the O–O bond of O2stretching to 1.46–1.48 Å equivalent to that of superoxide (•O2–), and •O2–is the predominant ROS responsible for As(III) oxidation. Our findings highlight the significant role of atom incorporation in changing the ET process on Fe(III) oxyhydroxides for ROS production. Thus, such an effect must be considered when evaluating Fe mineral reactivity toward changing their surface chemistry, such as those noted here for Cu incorporation, which likely determines the fates of arsenic and other redox sensitive pollutants in the environments with oscillating redox conditions.

This work presents the first example of acid/base-responsive and near-infrared (NIR)-absorbing photocatalysts based on imidazole-anion-fused perylene diimide chromophores. The photocatalysts were in situ generated by deprotonation of imidazole-fused perylene diimide under an alkaline environment. NIR (λ = 730 nm, 128 mW/cm2) photoinduced atom transfer radical polymerization (ATRP) was implemented, exhibiting high efficiency and excellent livingness under ppm level of photocatalysts (15 ppm relative to monomer) and Cu(II) complex (10 ppm relative to monomer) concentrations. The method showed capabilities to polymerize behind opaque barriers (i.e., paper and pig skin) and under aerobic condition. Notably, this work demonstrated a dual temporal control of polymerization by adding weak base/acid and switching NIR light on/off. The polymerization can even be halted by bubbling CO2and was then fully recovered by adding triethylamine. The NIR photoATRP of acrylamide monomers in aqueous solution was also performed, which can be regulated by the change of pH.

The rise of photoredox catalysis has extended the landscape of reversible-deactivation radical polymerization. Recently, visible-light-driven photoredox/Cu dual catalyzed atom transfer radical polymerization (photoATRP) has become an emerging trend, providing well-defined polymer under low copper catalyst loading. In this work, we described a dual catalyzed ATRP using CuBr2/tris(2-pyridinylmethyl)amine (TPMA) and donor–acceptor-type organophotoredox catalysts (OPCs) with visible light absorption. The excited state OPC can reduce both dormant polymer chain-end and CuBr2/TPMA, generating propagating radical species and CuBr/TPMA, respectively. This indicates that the mechanism is a hybrid of organophotoredox-mediated and Cu-mediated ATRP. The photoATRP driven by 425 nm light irradiation produced a series of well-defined polymethacrylates under extremely low catalyst loadings (5 or 10 ppm CuBr2and 1 ppm OPC relative to monomer). The method also showed excellent temporal control over polymerization and oxygen tolerance.

This paper provides a facile and cost-efficient method to prepare single-strand DNA (ssDNA) nanocone arrays and hierarchical DNA patterns that were mediated by poly(2-hydroxyethyl methacrylate) (PHEMA) brush. The PHEMA brush nanocone arrays with different morphology and period were fabricated via colloidal lithography. The hierarchical structure was prepared through the combination of colloidal lithography and traditional photolithography. The DNA patterns were easily achieved via grafting the amino group modified ssDNA onto the side chain of polymer brush, and the anchored DNA maintained their reactivity. The as-prepared ssDNA nanocone arrays can be applied for target DNA sensing with the detection limit reaching 1.65 nM. Besides, with the help of introducing microfluidic ideology, the hierarchical-multiplex DNA patterns on the same substrate could be easily achieved with each kind of pattern possessing one kind of ssDNA, which are promising surfaces for the preparation of rapid, visible, and multiplex DNA sensors.

The Graph Model for Conflict Resolution (GMCR) methodology is employed to ascertain strategic insights into a serious conflict over environmental concerns connected to the expanded exploitation of oil sands at the Jackpine Mine Expansion project located in Alberta, Canada. In fact, the expansion of extracting bitumen from large tracts of oil sands in Alberta and its associated potential negative environmental impacts have received increasing attention at the global level. Accordingly, environmentally responsible extended mining of bitumen at the Jackpine site is urgently needed. Hence, the GMCR methodology and its associated decision support system GMCR II are utilized to systematically investigate the conflict of the Jackpine Mine Expansion project. The results imply that the Federal Government of Canada is more concerned about the economic benefits generated by the oil sands projects rather than environmental impacts. It is suggested that more effort should be devoted to the environment conservation by the government.

To explore the value of ultrasonography in the auxiliary diagnosis of pleural effusion, we retrospectively analyzed the ultrasonographic findings of 275 exudates and 307 transudates and summarized the ultrasonographic image features of pleural effusion according to patients’ primary diseases. The findings of thoracic ultrasonography performed before the initial thoracentesis in 582 patients with subsequently confirmed exudative/transudative pleural effusion were analyzed with regard to the sonographic features of pleural effusion. In 275 cases with exudates, thoracic ultrasonography showed a complex septate appearance in 19 cases (6.9%), complex nonseptate appearance in 100 cases (36.4%), complex homogenous sign in 46 cases (16.7%), and pleural thickness > 3 mm in 105 cases. In contrast, in 307 patients with transudates, most patients (97.1%) had bilateral pleural effusion. Ultrasonographic images displayed anechoic appearance and absence of pleural thickening in a vast majority of cases (306, 99.7%; 301, 98%). These positive findings in the exudate were statistically higher than those in their counterparts (P< .05). In the empyema subgroup, the proportion of complex septate appearance, complex nonseptate appearance, complex homogenous sign, and pleural thickening was the highest, at 19/41, 12/41, 10/41, and 30/41, respectively. Ultrasonography is valuable in defining the nature of pleural effusion. Some sonographic features of pleural effusion, such as echogenicity, septation, and pleural thickening, may indicate a high risk of exudative pleural effusion.

The fabrication of versatile gold nanoparticle (Au NP) arrays with tunable optical properties by a novel host–guest interaction are presented. The gold nanoparticles were incorporated into polymer brushes by host–guest interaction between β-cyclodextrin (β-CD) ligand of gold nanoparticles and dimethylamino group of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA). The gold nanoparticle arrays were prepared through the template of PDMAEMA brush patterns which were fabricated combining colloidal lithography and surface-initiated atom-transfer radical polymerization (SI-ATRP). The structure parameters of gold nanoparticle patterns mediated by polymer brushes such as height, diameters, periods and distances, could be easily tuned by tailoring the etching time or size of colloidal spheres in the process of colloidal lithography. The change of optical properties induced by different gold nanoparticle structures was demonstrated. The direct utilization of PDMAEMA brushes as guest avoids a series of complicated modification process and the PDMAEMA brushes can be grafted on various substrates, which broaden its applications. The prepared gold naoparticle arrays are promising in applications of nanosensors, memory storage and surface enhanced spectroscopy.

This paper presents a novel method to fabricate elliptical ring arrays of proteins. The protein arrays are prepared by covalently grafting proteins to the polymer brush ring arrays which are prepared by the techniques combining colloidal lithography dewetting and surface initiated atom-transfer radical polymerization (SI-ATRP). Through this method, the parameters of protein patterns, such as height, wall thickness, periods, and distances between two elliptical rings, can be finely regulated. In addition, the sample which contains the elliptical protein ring arrays can be prepared over a large area up to 1 cm2, and the protein on the ring maintains its biological activity. The as-prepared ring and elliptical ring arrays (ERAs) of fibronectin can promote cell adhesion and may have an active effect on the formation of the actin cytoskeleton.

This paper presents a versatile way to prepare multiscale and gradient patterns of proteins. The protein patterns are fabricated by conjugating proteins covalently on patterns of polymer brush that are prepared by techniques combining colloidal lithography with photolithography, and two-step colloidal lithography. Taking advantages of this technique, the parameters of protein patterns, such as height, diameters, periods, and distances between two dots, can be arbitrarily tuned. In addition, the protein patterns with varies of architectures, such as microdiscs, microstripes, microrings, microtriangles, microgrids, etc., consisting of protein nanodots, are prepared and the sample size is up to 4 cm2. The as-prepared patterns of fibronectin can promote the cell adhesion and cell location.

In this Article, we report on plasmonic nanostructured surfaces with almost all colors by nanosphere lithography. The feature sizes of the plasmonic nanostructures can be controlled by O2reactive ion etching and gold evaporation conditions. The optical properties of the plasmonic nanostructured surfaces can be easily tuned in the visible light region by changing etching time, and the color of plasmonic nanostructured surfaces does not change with the viewing angle up to 45°. More importantly, such surfaces show high bulk sensitivity to the refractive index variation, and they can be used as label-free, real-time biosensors to detect biomacromolecules.

Recently, periadventitial adipose tissue (PAT) was found to secrete bioactive factors playing an important role in the regulation of vascular tension. Hydrogen sulfide (H2S), a novel cardiovascular gasotransmitter, relaxes vessels through the KATPchannel in a calcium-dependent and endothelial-independent manner.

Cocontamination with tetracycline (TC) and arsenic (As) is very common in paddy fields. However, the process and underlying mechanism of arsenite (As(III)) transformation on iron mineral surfaces in the presence of antibiotic contaminants remain unclear. In this study, the release and oxidation of As(III) on ferrihydrite (Fh) surfaces and Fh transformation in the presence of TC under both aerobic and anaerobic conditions were investigated. Our results indicated that the TC-induced reductive dissolution of Fh (Fe(II) release) and TC competitive adsorption significantly promote the release of As, especially under anaerobic conditions. The release of As was increased with increasing TC concentration, whereas it decreased with increasing pH. Interestingly, under both aerobic and anaerobic conditions, the addition of TC enhanced the oxidation of As(III) by Fh and induced the partial transformation of Fh to lepidocrocite. Under aerobic conditions, the adsorbed Fe(II) activated the production of reactive oxygen species (·OH and 1O2) from dissolved O2, with Fe(IV) being responsible for As(III) oxidation. Under anaerobic conditions, the abundant oxygen vacancies of Fh affected the oxidation of As(III) during Fh recrystallization. Thus, this study provided new insights into the role of TC on the migration and transformation of As coupled with Fe in soils.

Asthma is a common chronic lung disease without absolute treatment, and hypersensitivity reactions and type 2 immune responses are responsible for asthma pathophysiology. ADAM10 as a metalloproteinase transmembrane protein is critical for development of Th2 responses, and levamisole as an anthelmintic drug has immunomodulatory effects, which not only regulates ADAM10 activity but also can suppress the bone marrow and neutrophil production. Therefore, in the present study, nanoparticles were used as a levamisole delivery system to reduce bone marrow suppression, and the immunomodulatory and ADAM10 inhibitory effects of levamisole were studied in allergic asthma. Asthmatic mice were treated with PLGA-levamisole nanoparticles. Then, AHR, BALF, and blood cell counts, levels of the IgG1 subclass, total and OVA-specific IgE, IL2, IL-4, IL-5, IL-10, IL-13, IL-17, IL-25, IL-33, INF-γ, and TNF-α, gene expression of FoxP3, T-bet, RORγt, PU.1, GATA3, FcεRII, CysLT1R, eotaxin, and ADAM10, and lung histopathology were evaluated. PLGA-LMHCl with considered characteristics could control airway hyper-responsiveness, eosinophils in the BALF, levels of immunoglobulins, Th2-, Th9-, and Th17-derived cytokines and pivotal genes, eosinophilic inflammation, hyperplasia of the goblet cell, and hyperproduction of mucus and could increase Th1- and Treg-derived cytokines and also pivotal genes. It could also modulate the ADAM10 activity and had no effect on the number of neutrophils in the bloodstream. The novel safe nanodrug had no side effect on the bone marrow to produce neutrophils and could control the allegro-immuno-inflammatory response of asthma.

Increasingly, the world needs to know how to respond to challenges of environmental impact of a system composed of technologies, processes, and human activities. These environmental impacts result from human errors, system emissions (e.g., gases, radiations, sound, and dust), and waste that depletes resources (i.e., energy and materials) and/or endangers life. Therefore, this paper introduces terms and concepts used for evaluating the environmental reliability of a system. Moreover, considering environmental failure patterns (erratic, lumpy, intermittent, and smooth), human errors, and failure detection mechanisms (human sensory, monitoring device), several environmentally conscious models are developed to assess the environmental reliability of a system. Numerical examples are presented to demonstrate the application of the models.

Equity principles are embedded within a multiple objective framework for obtaining optimal solutions to a generic allocation problem, such as the fair distribution of water, energy, or other types of key resources among users in society. Because of the great import of fresh water as a scarce and diminishing resource within and among many nations of the world, the equity concepts are used in the allocation of water rights and subsequent water transfers or trades among users to improve the economic efficiency of water utilization. More specifically, water allocation is formulated as a generalized multiple objective problem and then the measurable fairness principles are used in the development of two approaches for equitable water rights allocation. In particular, the proposed priority-based maximal multiperiod network flow programming method has a social aggregation function satisfying the monotonicity and priority principles, and thus is a priority equitable allocation approach. The lexicographic minimax water shortage ratios method, which satisfies the principles of monotonicity, impartiality, and equitability, generates perfectly equitable solutions. The priority ranks and weights used in the two proposed approaches, respectively, are designed to achieve fair treatment of all the competitors for access to limited water resources and constitute important parameters. The capabilities of the approaches are tested and demonstrated in applications to the Aral Sea Basin in Central Asia and the South Saskatchewan River Basin in Western Canada.

A comprehensive decision support system called GMCA (Graph Model for Conflict Analysis) implementing the multi-player graph model for analyzing conflicts is developed. GMCA contains algorithms for the rapid computation of a wide range of solution concepts, thereby enabling decision makers to take account of the diversity of human behavior. Using an engineering case study, the key features of GMCA are illustrated.

The Graph Model for Conflict Resolution constitutes a unique and flexible approach to the representation, analysis, and understanding of strategic conflict. This methodology, as implemented in the Decision Support System GMCR, constitutes a useful tool for negotiation support. Because GMCR includes efficient algorithms for calculating the stability of states, it encourages extensive comparisons of the consequences of different models of negotiators' decision making. GMCR also facilitates modifications to the way in which the conflict is represented, encouraging sensitivity and what-if analyses. The applicability of GMCR to negotiations is discussed in general, and in the context of a specific case study in environmental conflict resolution.

A real-world application is employed to explain three general types of decision situations that can arise under conditions of conflict. In addition, meaningful connections and relationships among these areas of decision making are clearly pointed out. To permit useful decision technologies to be employed by practitioners for better understanding and for resolving a variety of actual decision problems, a range of flexible decision support systems is discussed. Subsequently, interesting research developments contained in the upcoming sequence of 12 articles on decision making under conflict are summarized and compared. The research articles not only present unique approaches to decision making involving multiple participants, each of whom may have multiple objectives, but suggest a variety of challenging research problems to be investigated in the future.

The Graph Model for Conflict Resolution is a flexible methodology for systematically studying strategic conflicts in the real world, and is therefore a natural tool for negotiation support. The basic definitions underlying the graph model are reviewed, and the techniques for analysis and interpretation are discussed. The modeling and analysis of a case study, an international trade negotiation concerning the export of Canadian softwood lumber to the United States, are used to demonstrate the practical application of the Graph Model for Conflict Resolution as a negotiation support tool. The modeling and analysis is carried out using the GMCR software system. The ability of the Graph Model for Conflict Resolution to provide insights and advice to negotiators is emphasized.

A comprehensive approach for modeling conflicts is the recently developed graph form of conflict model. The main objectives of this paper are to characterize various solution concepts using the graph model framework and to demonstrate how these developments are useful for modeling a real world dispute. The specific solution concepts formulated here for the graph model are Nash stability, metagame analysis, and the sequential stability approach of Fraser and Hipel. These solution concepts, and the limited-move and non-myopic methods developed previously, are compared and applied in this study. Finally, a complex international environmental dispute is analyzed to demonstrate the insight which decision makers can gain from studying a conflict using this methodology

Photoredox catalyzed atom transfer radical polymerization (photo-ATRP) has emerged as a fundamental and powerful polymerization method. Herein we report a class of facilely synthesized N-aryl phenoxazines that serves as highly efficient visible-light-driven photoredox organocatalysts. The strategy of thermally activated delayed fluorescence (TADF) was introduced with the organocatalysts by constructing an orthogonally linked D–A molecular configuration. The offset between the lowest singlet S1and lowest triplet T1excited states (ΔEST) is less than 0.30 eV in TADF molecules. The small ΔEST(<0.1 eV) and the long-lived excited states (>0.1 μs) of the organocatalysts were confirmed by theoretical and experimental studies. The combination of a strong electron donor and weak electron acceptors endows the molecules with high-lying HOMOs and LUMOs, which provide a sufficiently negative excited state reduction potential E0(PC•+/PC*) of ca. −1.5 V. The catalysts were applied in the photo-ATRP of methyl methacrylate using ethyl α-bromophenylacetate as the initiator under white-light irradiation. The photo-ATRP was successfully conducted with catalyst loadings as low as 30 ppm. The monomer scope was expanded to benzyl methacrylate (BnMA) and acrylate butyl methacrylate (BMA). Finally, the block polymer P(MMA-b-BnMA) was synthesized, demonstrating the high chain-end fidelity of the polymers.

Introduction: Elimination or blocking of astrocytes could ameliorate neuropathic pain in animal models. MiR-125a-5p, expressed in astrocyte derived extracellular vesicles, could mediate astrocyte function to regulate neuron communication. However, the role of miR-125a-5p in DPN (diabetic peripheral neuropathy) remains elusive.

The contact resistance between the cathodes and interconnects constitutes a significant part of the overall resistance in an SOFC stack. In order to enhance the conductibility between the cathode and interconnect, a new stack configuration of SOFC is proposed, with flexible contact layers of strontium-doped lanthanum manganite inserted to between the cathodes and interconnects as separated components. The conduct material is in fabric structure prepared from template via wet-chemical method. The preparation process and performance of the conduct material are described.

To explore cheap alternatives for platinum electrocatalysts, many strategies have been widely studied. And Pd is regarded as a ideal alternative catalyst due to its high stability and catalytic activity. In this work, we designed a facile method to prepare a highly efficient electrocatalyst in which ultrafine Pd nanoparticles are embedded into N-doped porous carbon nanosheets for oxygen reduction reaction (ORR) in alkaline and acid media. A series of products with different Pd quantities were in situ prepared in the absence of additional reductant and capping agents by varying the addition of PdCl2, while the morphology and the structural features of products through X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) and BET measurements show that Pd nanoparticles are embedded into N-doped porous carbon nanosheets. Obviously, the sample of Pd-NCs-3 demonstrate the best electrocatalytic activity and remarkable long-term stability among the series, which is superior to that of commercial Pd/C and comparable to that of commercial Pt/C for ORR in alkaline and acid media. The results provides a novel strategy for the rational development of cheap alternatives for platinum electrocatalysts.

We utilize a sliced slab waveguide structure to produce a gain waveguide array. With this array, an in-phase locked single-mode frequency output with a single-peak intensity distribution without sidelobes and a highly spatially suppressed far-field distribution has been obtained.