Synthesis of Janus polyaniline–polyelectrolyte complex membrane via in situ confined polymerization

Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P⁺:P^? represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P⁺ and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC–PANI exhibits asymmetric electrical property on different sides. © 2021 Society of Industrial Chemistry.     

Influence of physicochemical binder properties on agglomeration of wheat powder in couscous grain

Wet agglomeration mechanisms developing in low shear mixers have been described considering a fractal morphogenesis process that links the median size of the agglomerates with their solid volume fraction via a fractal dimension. It appears fundamental to integrate the polydispersity of the generated structures (nuclei, agglomerates, dough pieces) in the analysis of the agglomeration process in order to approach the industrial problems. The objective of this study is to correlate the influence of the physicochemical characteristics of several liquid binders, on the fractal agglomeration mechanisms. To do so, we considered the values of the fractal model parameters. The obtained results confirmed that semolina wet agglomeration follows a fractal morphogenesis for the different applied liquid binders. Our results also showed a marked influence of the studied physicochemical properties of the liquid binder on the value of the fractal model parameters. During wet agglomeration in low shear mixers, the mechanisms implied during agglomeration (wetting, nucleation and growth) do not occur consecutively, but they coexist throughout at each water contents.     

Early Stages of Recrystallization in Equal-Channel Angular Pressing (ECAP)-Deformed AA3104 Alloy Investigated Using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) Orientation Mappings

Early stages of recrystallization in alloys containing complex structure of second phase particles are of considerable practical interest. They were observed for the AA3104 alloy in which large particles occur against the background of randomly distributed dispersoids. The samples were deformed by equal channel angular pressing and then slightly annealed to obtain the state of partial recrystallization. The highly deformed alloy contained a structure of flat grains with the spacing between high-angle grain boundaries ranging from 100 nm to 1 ??m. On annealing, the structure coarsened and got transformed into nearly equiaxed grains by both discontinuous and continuous recrystallization. The nucleation of new grains was observed in statically recrystallized bulk samples using scanning electron microscopy, and during in-situ recrystallization in a transmission electron microscope. Special attention was paid to the nucleation of new grains in areas close to large second phase particles, where a relatively high stored energy was expected to stimulate nucleation. A particular role in the rise of nuclei is attributed to migration of low angle boundaries. During recrystallization at 623 K (350?°C), in most of the observed cases, the growth of grains occurred by coalescence of neighbouring cells and by migration of high-angle grain boundaries. These processes led to nearly equiaxed grains of similar size. Orientation mappings showed that although orientations of new grains were widely scattered, they were not completely random.     

Motion planning algorithms for molecular simulations: A survey

Motion planning is a fundamental problem in robotics that has motivated research since more than three decades ago. A large variety of algorithms have been proposed to compute feasible motions of multi-body systems in constrained workspaces. In recent years, some of these algorithms have surpassed the frontiers of robotics, finding applications in other domains such as industrial manufacturing, computer animation and computational structural biology. This paper concerns the latter domain, providing a survey on motion planning algorithms applied to molecular modeling and simulation. Both the algorithmic and application sides are discussed, as well as the different issues to be taken into consideration when extending robot motion planning algorithms to deal with molecules. From an algorithmic perspective, the paper gives a general overview of the different extensions to sampling-based motion planners. From the point of view of applications, the survey deals with problems involving protein folding and conformational transitions, as well as protein–ligand interactions.     

The behavior of statically-indeterminate structural members and frames with cracks present

Crack stability is discussed as affected by their presence in statically-indeterminate beams, frames, rings, etc. loaded into the plastic range. The stability of a crack in a section, which has become plastic, is analyzed with the remainder of the structure elastic and with subsequent additional plastic hinges occurring. The reduction of energy absorption characteristics for large deformations is also discussed. The methods of elastic-plastic tearing instability are incorporated to show that in many cases the fully plastic collapse mechanism must occur for complete failure.     

Multi-level integrated planning and greening of public infrastructure in South Africa

The South African government has named the transition towards a greener economy one of its priorities. Meanwhile it has developed a new multilevel integrated planning process, and announced a massive public infrastructure investment plan. The converging point of these three dynamics should be the integration of green infrastructure principles into the different plans as the foundation of the green transition. This paper uses a policy integration analytical framework to assess whether this convergence is in fact taking shape. It analyses the level of integration of green infrastructure principles into the different plans and suggests options to move the green infrastructure agenda forward.     

Discovery of Highly Potent Dual Orexin Receptor Antagonists via a Scaffold‐Hopping Approach

Starting from suvorexant (trade name Belsomra), we successfully identified interesting templates leading to potent dual orexin receptor antagonists (DORAs) via a scaffold‐hopping approach. Structure–activity relationship optimization allowed us not only to improve the antagonistic potency on both orexin 1 and orexin 2 receptors (Ox1 and Ox2, respectively), but also to increase metabolic stability in human liver microsomes (HLM), decrease time‐dependent inhibition of cytochrome P450 (CYP) 3A4, and decrease P‐glycoprotein (Pgp)‐mediated efflux. Compound 80 c [{(1S,6R)‐3‐(6,7‐difluoroquinoxalin‐2‐yl)‐3,8‐diazabicyclo[4.2.0]octan‐8‐yl}(4‐methyl‐[1,1′‐biphenyl]‐2‐yl)methanone] is a potent and selective DORA that inhibits the stimulating effects of orexin peptides OXA and OXB at both Ox1 and Ox2. In calcium‐release assays, 80 c was found to exhibit an insurmountable antagonistic profile at both Ox1 and Ox2, while displaying a sleep‐promoting effect in rat and dog models, similar to that of the benchmark compound suvorexant.     

Synthesis and Microstructural Characterization of Substoichiometric Ti2Al(CxNy) Solid Solutions and Related Ti2AlCx and Ti2AlN End‐Members

Ti, TiC, Al and AlN powders were mixed to synthesize Ti₂Al(C_xN_y) (x + y < 1) solid solutions, Ti₂AlC_x (x < 1) and Ti₂AlN‐related end‐members by hot isostatic pressing at 1400°C/80 MPa for 4 h. For the pure carbides, it is demonstrated that single‐phased samples can only be obtained when about 15% of substoichiometry on the carbon site is applied. Such a result likely implies that Ti₂AlC_x can only exist in a narrow range of carbon composition. Ti₂AlN nitride can be synthesized with y = 1. Assuming that vacancy content varies linearly from 0 to 0.15 going from Ti₂AlN to Ti₂AlC_0.85 in the solid solutions, element concentrations have been calculated to synthesize different solid solutions. Thus, it is demonstrated that single‐phased and fully dense Ti₂Al(C_0.23N_0.71), Ti₂Al(C_0.45N_0.45), and Ti₂Al(C_0.66N_0.22) carbonitrides can be synthesized.     

Analysis of the Shrinkage Effect on Mass Transfer During Convective Drying of Sawdust/Sludge Mixtures

Convective drying of wastewater sludges and sawdust/sludge mixtures was studied. The first part of this work was an experimental study performed in a cross-flow convective dryer using 500 g of wet material extruded through a disk with circular dies of 12 mm. The results showed that the sawdust addition has a positive impact on the drying process from a mass ratio of 2/8, on a dry basis, with observed drying rates higher than the original sludge. The second part of this work consisted of developing a drying model in order to identify the internal diffusion coefficient and convective mass transfer coefficient from the experimental data. A comparison was made between fitted drying curves, well represented by the Newton's model, and the analytical solutions of the diffusion equation applied to a finite cylinder. Variations of dimensional characteristics, such as the volume and exchange surface of the sample bed, were obtained by X-ray tomography. This technique allowed us to confirm that shrinkage, which is an important phenomenon occurring during sludge and sawdust/sludge mixture drying, must be taken into account. The results showed that both the internal diffusion coefficient and convective mass transfer coefficient were affected by mixing and sawdust addition. The internal diffusion coefficient changed from 7.77 × 10^?9 m²/s for the original sludge to 7.01 × 10^?9 m²/s for the mixed sludge and then increased to 8.35 × 10^?9 m²/s for the mixture of a mass ratio of 4/6. The convective mass transfer coefficient changed from 9.70 × 10^?8 m/s for the original sludge to 8.67 × 10^?8 m/s for the mixed sludge and then increased to 12.09 × 10^?8 m/s for the mixture of a mass ratio of 4/6. These results confirmed that sawdust addition was beneficial to the sludge drying process as the mass transfer efficiency between the air and material increased. Reinforcing the texture of sludge by adding sawdust can increase the drying rate and decrease the drying time, and then the heat energy supply will be reduced significantly. The study also showed that neglecting shrinkage phenomenon resulted in an overestimation for the internal diffusion coefficient for the convective drying of sludges and sawdust/sludge mixtures.     

Molecular Networking for Drug Toxicities Studies: The Case of Hydroxychloroquine in COVID-19 Patients

Using drugs to treat COVID-19 symptoms may induce adverse effects and modify patient outcomes. These adverse events may be further aggravated in obese patients, who often present different illnesses such as metabolic-associated fatty liver disease. In Rennes University Hospital, several drug such as hydroxychloroquine (HCQ) have been used in the clinical trial HARMONICOV to treat COVID-19 patients, including obese patients. The aim of this study is to determine whether HCQ metabolism and hepatotoxicity are worsened in obese patients using an in vivo/in vitro approach. Liquid chromatography high resolution mass spectrometry in combination with untargeted screening and molecular networking were employed to study drug metabolism in vivo (patient’s plasma) and in vitro (HepaRG cells and RPTEC cells). In addition, HepaRG cells model were used to reproduce pathophysiological features of obese patient metabolism, i.e., in the condition of hepatic steatosis. The metabolic signature of HCQ was modified in HepaRG cells cultured under a steatosis condition and a new metabolite was detected (carboxychloroquine). The RPTEC model was found to produce only one metabolite. A higher cytotoxicity of HCQ was observed in HepaRG cells exposed to exogenous fatty acids, while neutral lipid accumulation (steatosis) was further enhanced in these cells. These in vitro data were compared with the biological parameters of 17 COVID-19 patients treated with HCQ included in the HARMONICOV cohort. Overall, our data suggest that steatosis may be a risk factor for altered drug metabolism and possibly toxicity of HCQ.