Controlled Localized Metal-Organic Framework Synthesis on Anion Exchange Membranes.

Metal-organic framework (MOF) films can be used in various applications. In this work, we propose a method that can be used to synthesize MOF films localized on a single side of an anion exchange membrane, preventing the transport of the metal precursor via Donnan exclusion. This is advantageous compared to the related contra-diffusion method that results in the growth of a MOF film on both sides of the support, differing in quality on both sides. Our proposed method has the advantage that the synthesis conditions can potentially be tuned to create the optimal conditions for crystal growth on a single side. The localized growth of the MOF is governed by Donnan exclusion of the anion exchange membrane, preventing metal ions from passing to the other compartment, and this leads to a local control of the precursor stoichiometry. In this work, we show that our method can localize the growth of both Cu-BTC and ZIF-8 in water and in methanol, respectively, highlighting that this method can used for preparing a variety of MOF films with varying characteristics using soluble precursors at room temperature.

Sludge degradation, nutrient removal and reduction of greenhouse gas emission by a Chironomus-Azolla wastewater treatment cascade.

Wastewater treatment plants (WWTPs) are a point source of nutrients, emit greenhouse gases (GHGs), and produce large volumes of excess sludge. The use of aquatic organisms may be an alternative to the technical post-treatment of WWTP effluent, as they play an important role in nutrient dynamics and carbon balance in natural ecosystems. The aim of this study was therefore to assess the performance of an experimental wastewater-treatment cascade of bioturbating macroinvertebrates and floating plants in terms of sludge degradation, nutrient removal and lowering GHG emission. To this end, a full-factorial experiment was designed, using a recirculating cascade with a WWTP sludge compartment with or without bioturbating Chironomus riparius larvae, and an effluent container with or without the floating plant Azolla filiculoides, resulting in four treatments. To calculate the nitrogen (N), phosphorus (P) and carbon (C) mass balance of this system, the N, P and C concentrations in the effluent, biomass production, and sludge degradation, as well as the N, P and C content of all compartments in the cascade were measured during the 26-day experiment. The presence of Chironomus led to an increased sludge degradation of 44% compared to 25% in the control, a 1.4 times decreased transport of P from the sludge and a 2.4 times increased transport of N out of the sludge, either into Chironomus biomass or into the water column. Furthermore, Chironomus activity decreased methane emissions by 92%. The presence of Azolla resulted in a 15% lower P concentration in the effluent than in the control treatment, and a CO2 uptake of 1.13 kg ha-1 day-1. These additive effects of Chironomus and Azolla resulted in an almost two times higher sludge degradation, and an almost two times lower P concentration in the effluent. This is the first study that shows that a bio-based cascade can strongly reduce GHG and P emissions simultaneously during the combined polishing of wastewater sludge and effluent, benefitting from the additive effects of the presence of both macrophytes and invertebrates. In addition to the microbial based treatment steps already employed on WWTPs, the integration of higher organisms in the treatment process expands the WWTP based ecosystem and allows for the inclusion of macroinvertebrate and macrophyte mediated processes. Applying macroinvertebrate-plant cascades may therefore be a promising tool to tackle the present and future challenges of WWTPs.

Wastewater treatment plant contaminant profiles affect macroinvertebrate sludge degradation.

Disposal of the overwhelming amounts of excess wastewater treatment plant (WWTP) sludge is an increasing financial and environmental problem, and new methods to reduce the amount of excess sludge are therefore required. In the natural environment, interactions between multiple macroinvertebrate detritivores mediate the degradation of organic matter. Macroinvertebrates may thus also be able to degrade WWTP sludge, but may meanwhile be impacted by the associated contaminants. Therefore, the aim of the present study was to examine if WWTPs contaminant concentrations and profiles affect the biotic interactions and macroinvertebrate mediated degradation of sludge. Assessing degradation of sludge from three WWTPs differing in contaminant profile by (combinations of) three macroinvertebrate detritovore taxa, revealed that macroinvertebrate enhanced sludge degradation was WWTP and taxa combination specific. Yet, taxa combinations only had an additional positive effect on sludge degradation when compared to single taxa in sludge with a higher contaminant load. This was confirmed by the results of a Cu-spiked sludge degradation experiment, indicating a possible effect of biotic interactions. It was concluded that macroinvertebrates are a potential tool for the reduction of excess WWTP sludge, and that using multispecies assemblages of detritivorous macroinvertebrates may increase the resilience of this additional treatment step.

Organic matter degradation and redistribution of sediment associated contaminants by benthic invertebrate activities.

The fate of sediment associated compounds is the combined result of chemical properties and biological activities. Yet, studies simultaneously addressing the effects of biota on the redistribution and bioaccumulation of contaminants are scarce. Our aim was therefore to assess the effect of benthic invertebrate activities on organic matter degradation and the redistribution of metals and Polycyclic Aromatic Hydrocarbons (PAHs) in contaminated sediment. To this end, we introduced egg ropes of the non-biting midge Chironomus riparius into wastewater treatment plant sludge and allowed these to either develop until fourth instar larvae or to fully complete their life cycle into terrestrial flying adults. Chironomid larvae enhanced sludge degradation, resulting in increased metal concentrations in the sludge and in a flux of metals into the overlying water. Moreover, they hampered PAH degradation in the sludge. Contaminant transport from aquatic to terrestrial ecosystems with emerging invertebrates as a vector is widely acknowledged, but here we showed that biomanipulation prevailed over bioaccumulation, since due to chironomid activity, the flux of metals from the sludge into the overlying water was larger than into chironomid biomass. It is therefore concluded that contaminant-macroinvertebrate interactions are bilateral relationships driven by the interplay between macroinvertebrate traits and contaminant properties.

Chemical Genetics Approach Identifies Abnormal Inflorescence Meristem 1 as a Putative Target of a Novel Sulfonamide That Protects Catalase2-Deficient Arabidopsis against Photorespiratory Stress.

Alterations of hydrogen peroxide (H2O2) levels have a profound impact on numerous signaling cascades orchestrating plant growth, development, and stress signaling, including programmed cell death. To expand the repertoire of known molecular mechanisms implicated in H2O2 signaling, we performed a forward chemical screen to identify small molecules that could alleviate the photorespiratory-induced cell death phenotype of Arabidopsisthaliana mutants lacking H2O2-scavenging capacity by peroxisomal catalase2. Here, we report the characterization of pakerine, an m-sulfamoyl benzamide from the sulfonamide family. Pakerine alleviates the cell death phenotype of cat2 mutants exposed to photorespiration-promoting conditions and delays dark-induced senescence in wild-type Arabidopsis leaves. By using a combination of transcriptomics, metabolomics, and affinity purification, we identified abnormal inflorescence meristem 1 (AIM1) as a putative protein target of pakerine. AIM1 is a 3-hydroxyacyl-CoA dehydrogenase involved in fatty acid ß-oxidation that contributes to jasmonic acid (JA) and salicylic acid (SA) biosynthesis. Whereas intact JA biosynthesis was not required for pakerine bioactivity, our results point toward a role for ß-oxidation-dependent SA production in the execution of H2O2-mediated cell death.

How Plants Sense and Respond to Stressful Environments.

Plants are exposed to an ever-changing environment to which they have to adjust accordingly. Their response is tightly regulated by complex signaling pathways that all start with stimulus perception. Here, we give an overview of the latest developments in the perception of various abiotic stresses, including drought, salinity, flooding, and temperature stress. We discuss whether proposed perception mechanisms are true sensors, which is well established for some abiotic factors but not yet fully elucidated for others. In addition, we review the downstream cellular responses, many of which are shared by various stresses but result in stress-specific physiological and developmental output. New sensing mechanisms have been identified, including heat sensing by the photoreceptor phytochrome B, salt sensing by glycosylinositol phosphorylceramide sphingolipids, and drought sensing by the specific calcium influx channel OSCA1. The simultaneous occurrence of multiple stress conditions shows characteristic downstream signaling signatures that were previously considered general signaling responses. The integration of sensing of multiple stress conditions and subsequent signaling responses is a promising venue for future research to improve the understanding of plant abiotic stress perception.

Molecular priming as an approach to induce tolerance against abiotic and oxidative stresses in crop plants.

Abiotic stresses, including drought, salinity, extreme temperature, and pollutants, are the main cause of crop losses worldwide. Novel climate-adapted crops and stress tolerance-enhancing compounds are increasingly needed to counteract the negative effects of unfavorable stressful environments. A number of natural products and synthetic chemicals can protect model and crop plants against abiotic stresses through induction of molecular and physiological defense mechanisms, a process known as molecular priming. In addition to their stress-protective effect, some of these compounds can also stimulate plant growth. Here, we provide an overview of the known physiological and molecular mechanisms that induce molecular priming, together with a survey of the approaches aimed to discover and functionally study new stress-alleviating chemicals.

Domino reaction of a gold catalyzed 5-endo-dig cyclization and a [3,3]-sigmatropic rearrangement towards polysubstituted pyrazoles.

Pyrazoles are important heterocyclic compounds with a broad range of biological activities. A new procedure toward tri- or tetrasubstituted pyrazoles has been developed, via a one-pot gold catalyzed synthesis from hydrazines with alkynyl aldehydes or ketones. The reaction proceeds through consecutive hydrazone formation, 5-endo-dig cyclization and an aza-Claisen rearrangement resulting in the desired polysubstitued pyrazoles.

Mediated Leader Effects: The Impact of Newspapers' Portrayal of Party Leadership on Electoral Support.

Conventional wisdom holds that party leaders matter in democratic elections. As very few voters have direct contact with party leaders, media are voters' primary source of information about these leaders and, thus, the likely origin of leader effects on party support. Our study focuses on these supposed electoral effects of the media coverage of party leaders. We examine the positive and negative effects of specific leadership images in Dutch newspapers on vote intentions. To this end, we combine an extensive automated content analysis of leadership images in the media with a panel data set, the Dutch 1Vandaag Opinion Panel (1VOP), consisting of more than fifty thousand unique respondents and 110 waves of interviews conducted between September 2006 and September 2012. The results confirm that media coverage of party leaders' character traits affects voters: Positive mediated leadership images increase support for the leader's party, while negative images decrease this support. However, this influence is not unconditional: During campaign periods, positive leadership images have a stronger effect, while negative images no longer have an impact on subsequent vote intentions.

Sex- and Dose-Specific Effects of Maternal Bisphenol A Exposure on Pancreatic Islets of First- and Second-Generation Adult Mice Offspring.

BACKGROUND: Exposure to the environmental endocrine disruptor bisphenol A (BPA) is ubiquitous and associated with the increased risk of diabetes and obesity. However, the underlying mechanisms remain unknown. We recently demonstrated that perinatal BPA exposure is associated with higher body fat, impaired glucose tolerance, and reduced insulin secretion in first- (F1) and second-generation (F2) C57BL/6J male mice offspring. OBJECTIVE: We sought to determine the multigenerational effects of maternal bisphenol A exposure on mouse pancreatic islets. METHODS: Cellular and molecular mechanisms underlying these persistent changes were determined in F1 and F2 adult offspring of F0 mothers exposed to two relevant human exposure levels of BPA (10µg/kg/d-LowerB and 10mg/kg/d-UpperB). RESULTS: Both doses of BPA significantly impaired insulin secretion in male but not female F1 and F2 offspring. Surprisingly, LowerB and UpperB induced islet inflammation in male F1 offspring that persisted into the next generation. We also observed dose-specific effects of BPA on islets in males. UpperB exposure impaired mitochondrial function, whereas LowerB exposure significantly reduced ß-cell mass and increased ß-cell death that persisted in the F2 generation. Transcriptome analyses supported these physiologic findings and there were significant dose-specific changes in the expression of genes regulating inflammation and mitochondrial function. Previously we observed increased expression of the critically important ß-cell gene, Igf2 in whole F1 embryos. Surprisingly, increased Igf2 expression persisted in the islets of male F1 and F2 offspring and was associated with altered DNA methylation. CONCLUSION: These findings demonstrate that maternal BPA exposure has dose- and sex-specific effects on pancreatic islets of adult F1 and F2 mice offspring. The transmission of these changes across multiple generations may involve either mitochondrial dysfunction and/or epigenetic modifications. https://doi.org/10.1289/EHP1674.

Continent of pessimism or continent of realism? A multilevel study into the impact of macro-economic outcomes and political institutions on societal pessimism, European Union 2006-2012.

The often-posed claim that Europe is a pessimistic continent is not unjustified. In 2012, 53 percent of European Union (EU) citizens were pessimistic about their country. Surprisingly, however, societal pessimism has received very little scientific attention. In this article, we examine to what extent political and economic factors drive societal pessimism. In terms of political factors, we expect that supranationalization, political instability, and corruption increase societal pessimism, as they diminish national political power and can inspire collective powerlessness. Economically, we expect that the retrenchment of welfare state provisions and economic decline drive societal pessimism, as these developments contribute to socioeconomic vulnerability. We assess the impact of these political and economic factors on the level of societal pessimism in the EU, both cross-nationally and over time, through multilevel analyses of Eurobarometer data (13 waves between 2006 and 2012 in 23 EU countries). Our findings show that the political factors (changes in government, corruption) primarily explain cross-national differences in societal pessimism, while the macro-economic context (economic growth, unemployment) primarily explains longitudinal trends within countries. These findings demonstrate that, to a large extent, societal pessimism cannot be viewed separately from its political and economic context.

A chemoselective and continuous synthesis of m-sulfamoylbenzamide analogues.

For the synthesis of m-sulfamoylbenzamide analogues, small molecules which are known for their bioactivity, a chemoselective procedure has been developed starting from m-(chlorosulfonyl)benzoyl chloride. Although a chemoselective process in batch was already reported, a continuous-flow process reveals an increased selectivity at higher temperatures and without catalysts. In total, 15 analogues were synthesized, using similar conditions, with yields ranging between 65 and 99%. This is the first automated and chemoselective synthesis of m-sulfamoylbenzamide analogues.

Low-Phosphate Induction of Plastidal Stromules Is Dependent on Strigolactones But Not on the Canonical Strigolactone Signaling Component MAX2.

Stromules are highly dynamic protrusions of the plastids in plants. Several factors, such as drought and light conditions, influence the stromule frequency (SF) in a positive or negative way. A relatively recently discovered class of plant hormones are the strigolactones; strigolactones inhibit branching of the shoots and promote beneficial interactions between roots and arbuscular mycorrhizal fungi. Here, we investigate the link between the formation of stromules and strigolactones. This research shows a strong link between strigolactones and the formation of stromules: SF correlates with strigolactone levels in the wild type and strigolactone mutants (max2-1 max3-9), and SF is stimulated by strigolactone GR24 and reduced by strigolactone inhibitor D2.

Neither bridging nor bonding: A test of socialization effects by ethnically diverse voluntary associations on participants' inter-ethnic tolerance, inter-ethnic trust and intra-ethnic belonging.

The distinction between bridging and bonding associations is a cornerstone of social capital research. Nevertheless, this study is the first to provide a direct test of the socialization mechanism that supposedly causes ethnically mixed (bridging) associations to generate interethnic tolerance and trust, and homogenous (bonding) associations to cement self-affirming identities. This multilevel analysis of the Citizenship, Involvement & Democracy (CID) 1999/2000 survey data on Mannheim (Germany), Enschede (the Netherlands), and Aberdeen (Scotland) covers 3166 active participants in 645 associations. The CID includes objective, exogenous measures of each association's composition and aim. Socialization and self-selection effects are pulled apart through interactions with detailed measures of associational involvement. The results display no evidence for (diverse and homogenous) associations as socializing agents. Although inter-ethnic tolerance is higher in ethnically diverse associations, this should be attributed to self-selection effects.