In Situ Small-Angle X-ray Scattering Studies During Reversible Addition–Fragmentation Chain Transfer Aqueous Emulsion Polymerization

Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016, 7, 5078–5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization

Novel techniques for automorphism group computation

Graph automorphism (GA) is a classical problem, in which the objective is to compute the automorphism group of an input graph. In this work we propose four novel techniques to speed up algorithms that solve the GA problem by exploring a search tree. They increase the performance of the algorithm by allowing to reduce the depth of the search tree, and by effectively pruning it. We formally prove that a GA algorithm that uses these techniques correctly computes the automorphism group of the input graph. We also describe how the techniques have been incorporated into the GA algorithm conauto, as conauto-2.03, with at most an additive polynomial increase in its asymptotic time complexity. We have experimentally evaluated the impact of each of the above techniques with several graph families. We have observed that each of the techniques by itself significantly reduces the number of processed nodes of the search tree in some subset of graphs, which justifies the use of each of them. Then, when they are applied together, their effect is combined, leading to reductions in the number of processed nodes in most graphs. This is also reflected in a reduction of the running time, which is substantial in some graph families

Unemployment Insurance and Low-Educated Single Working Mothers Before and After Welfare Reform

Using the Survey of Income and Program Participation (SIPP), a nationally representative, longitudinal survey, this study examines changing levels of Unemployment Insurance (UI) eligibility and benefit receipt among working low-educated single mothers, 1990–2005. It also examines changing participation in cash welfare and the Food Stamp Program (FSP). Relative to single childless women, there has been no increase in UI benefit receipt among single mothers entering a spell of unemployment in the postreform period, even though single mothers have increased their relative rates of UI eligibility. Because of declining cash assistance receipt, UI became a more common income support than cash assistance for this population during the period 2001–2005. Furthermore, the probability of accessing FSP for low-educated single mothers entering a spell of unemployment increased in the years 2001–2005. As a result, the proportion of this population accessing benefits from one or more of these programs remained virtually unchanged across the study period

Extending SMT Solvers to Higher-Order Logic

International audienceSMT solvers have throughout the years been able to cope with increasingly expressive formulas, from ground logics to full first-order logic (FOL). In contrast, the extension of SMT solvers to higher-order logic (HOL) is mostly un-explored. We propose a pragmatic extension for SMT solvers to support HOL reasoning natively without compromising performance on FOL reasoning, thus leveraging the extensive research and implementation efforts dedicated to efficient SMT solving. We show how to generalize data structures and the ground decision procedure to support partial applications and extensionality, as well as how to reconcile quantifier instantiation techniques with higher-order variables. We also discuss a separate approach for redesigning an HOL SMT solver from the ground up via new data structures and algorithms. We apply our pragmatic extension to the CVC4 SMT solver and discuss a redesign of the veriT SMT solver. Our evaluation shows they are competitive with state-of-the-art HOL provers and often outperform the traditional encoding into FOL

The fate and behavior of selected endocrine disrupting chemicals in full scale wastewater and sludge treatment unit processes

Endocrine disrupting chemicals are discharged into the environment mainly through wastewater treatment processes. There is a need for better understanding of the fate of these compounds in the unit processes of treatment plant to optimize their removal. The fate of oestrone, 17β-estradiol, 17α-ethinyestradiol and nonylphenol in the unit processes of full scale wastewater treatment plants in the UK, including activated sludge plant, oxidation ditch, biofilter and rotating biological contractor were investigated. The overall removal efficiencies of all the compounds ranged from 41 % to 100 %. The removals were predominantly during the secondary biological treatment with the rates of removal related to the nitrification rates and the sludge age. The removal efficiency of the treatment processes were in the order activated sludge > oxidation ditch > biofilter > rotating biological contractors. Activated sludge plant configured for biological nutrient removal showed better removal of the endocrine disrupting chemicals compared to conventional activated sludge plant effluents. Tertiary treatment was also significant in the removal process through solids removal. Overall mechanisms of removal were biodegradation and sorption unto sludge biomass. Phytoremediation was also significant in the removal processes. The endocrine disrupting chemicals persisted in the anaerobic sludge digestion process with percentage removals ranging fro 10-48 %. Sorption of the endocrine disrupting chemicals onto the sludge increased with increasing values for the partitioning coefficients and the organic carbon contents of the sludge

Long-Term Cold Acclimation Extends Survival Time at 0°C and Modifies the Metabolomic Profiles of the Larvae of the Fruit Fly Drosophila melanogaster

Drosophila melanogaster is a chill-susceptible insect. Previous studies on this fly focused on acute direct chilling injury during cold shock and showed that lower lethal temperature (LLT, approximately -5°C) exhibits relatively low plasticity and that acclimations, both rapid cold hardening (RCH) and long-term cold acclimation, shift the LLT by only a few degrees at the maximum.We found that long-term cold acclimation considerably improved cold tolerance in fully grown third-instar larvae of D. melanogaster. A comparison of the larvae acclimated at constant 25°C with those acclimated at constant 15°C followed by constant 6°C for 2 d (15°C→6°C) showed that long-term cold acclimation extended the lethal time for 50% of the population (Lt(50)) during exposure to constant 0°C as much as 630-fold (from 0.137 h to 86.658 h). Such marked physiological plasticity in Lt(50) (in contrast to LLT) suggested that chronic indirect chilling injury at 0°C differs from that caused by cold shock. Long-term cold acclimation modified the metabolomic profiles of the larvae. Accumulations of proline (up to 17.7 mM) and trehalose (up to 36.5 mM) were the two most prominent responses. In addition, restructuring of the glycerophospholipid composition of biological membranes was observed. The relative proportion of glycerophosphoethanolamines (especially those with linoleic acid at the sn-2 position) increased at the expense of glycerophosphocholines.Third-instar larvae of D. melanogaster improved their cold tolerance in response to long-term cold acclimation and showed metabolic potential for the accumulation of proline and trehalose and for membrane restructuring