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.     

Scallops as a new source of food protein: high-intensity ultrasonication improved stability of oil-in-water emulsion stabilised by myofibrillar protein

In this study, the effect of high-intensity ultrasound (HIUS) (200 and 400 W for 0, 5, 10 and 15 min respectively) on conformational changes, physicochemical, rheological and emulsifying properties of scallop (Patinopecten yessoensis) myofibrillar protein (SMP) was investigated. HIUS-treated SMP had lower α-helix content and higher β-sheet content compared with the native SMP. HIUS treatment induced the unfolding of SMP and increased the surface hydrophobicity. The particle size of SMP decreased and the absolute zeta-potential increased after ultrasonication, which in turn increased the solubility of SMP. The conformational changes and the improvement of physicochemical properties of SMP increased the ability for SMP to lower the interfacial tension at the oil–water interface and increased the percentage of adsorbed protein. As a result, the emulsifying properties, rheological properties of SMP and storage stability of emulsions were also improved. In conclusion, HIUS treatment has future potential for improving the emulsifying properties of SMP.     

Advanced Understanding of the Electron Transfer Pathway of Cytochrome P450s

Cytochrome P450s are heme-thiolate enzymes that participate in carbon source assimilation, natural compound biosynthesis and xenobiotic metabolism in all kingdoms of life. P450s can catalyze various reactions by using a wide range of organic compounds, thus exhibiting great potential in biotechnological applications. The catalytic reactions of P450s are driven by electron equivalents that are sourced from pyridine nucleotides and delivered by cognate or matching redox partners (RPs). The electron transfer (ET) route from RPs to P450s involves one or more redox center-containing domains. As the rate of ET is one of the main determinants of P450 efficacy, an in-depth understanding of the P450 ET pathway should increase our knowledge of these important enzymes and benefit their further applications. Here, the various P450 RP systems along with current understanding of their ET routes will be reviewed. Notably, state-of-the-art structural studies of the two main types of self-sufficient P450 will also be summarized.     

Coupling Interrupted Fischer and Multicomponent Joullié-Ugi to Chase Chemical Diversity: from Batch to Sustainable Flow Synthesis of Peptidomimetics

The generation of peptidomimetic substructures for medicinal chemistry purposes requires effective and divergent synthetic methods. We present in this work an efficient flow process that allows quick modulation of reagents for Joullié-Ugi multicomponent reaction, using spiroindolenines as core motifs. This sterically hindered imine equivalent could successfully be diversified using various isocyanides and amino acids in generally good space-time yields. A telescoped flow process combining interrupted Fischer reaction for spiroindolenine synthesis and subsequent Joullié-Ugi-type modification resulted in product formation in very good overall yield in less than 2 hours compared to 48 hours required in batch mode. The developed protocol can be seen as a general tool for rapid and facile generation of peptidomimetic compounds. We also showcase preliminary biological assessments for the prepared compounds.     

Direct View on the Origin of High Li+ Transfer Impedance in All-Solid-State Battery

Large interfacial resistance plays a dominant role in the performance of all-solid-state lithium-ion batteries. However, the mechanism of interfacial resistance has been under debate. Here, the Li⁺ transport at the interfacial region is investigated to reveal the origin of the high Li⁺ transfer impedance in a LiCoO₂(LCO)/LiPON/Pt all-solid-state battery. Both an unexpected nanocrystalline layer and a structurally disordered transition layer are discovered to be inherent to the LCO/LiPON interface. Under electrochemical conditions, the nanocrystalline layer with insufficient electrochemical stability leads to the introduction of voids during electrochemical cycles, which is the origin of the high Li⁺ transfer impedance at solid electrolyte-electrode interfaces. In addition, at relatively low temperatures, the oxygen vacancies migration in the transition layer results in the formation of Co₃O₄ nanocrystalline layer with nanovoids, which contributes to the high Li⁺ transfer impedance. This work sheds light on the mechanism for the high interfacial resistance and promotes overcoming the interfacial issues in all-solid-state batteries.     

Idiosyncratic Drug-Induced Liver Injury: Mechanistic and Clinical Challenges

Idiosyncratic drug-induced liver injury (IDILI) remains a significant problem for patients and drug development. The idiosyncratic nature of IDILI makes mechanistic studies difficult, and little is known of its pathogenesis for certain. Circumstantial evidence suggests that most, but not all, IDILI is caused by reactive metabolites of drugs that are bioactivated by cytochromes P450 and other enzymes in the liver. Additionally, there is overwhelming evidence that most IDILI is mediated by the adaptive immune system; one example being the association of IDILI caused by specific drugs with specific human leukocyte antigen (HLA) haplotypes, and this may in part explain the idiosyncratic nature of these reactions. The T cell receptor repertoire likely also contributes to the idiosyncratic nature. Although most of the liver injury is likely mediated by the adaptive immune system, specifically cytotoxic CD8+ T cells, adaptive immune activation first requires an innate immune response to activate antigen presenting cells and produce cytokines required for T cell proliferation. This innate response is likely caused by either a reactive metabolite or some form of cell stress that is clinically silent but not idiosyncratic. If this is true it would make it possible to study the early steps in the immune response that in some patients can lead to IDILI. Other hypotheses have been proposed, such as mitochondrial injury, inhibition of the bile salt export pump, unfolded protein response, and oxidative stress although, in most cases, it is likely that they are also involved in the initiation of an immune response rather than representing a completely separate mechanism. Using the clinical manifestations of liver injury from a number of examples of IDILI-associated drugs, this review aims to summarize and illustrate these mechanistic hypotheses.     

Effects of carbon nanotubes and interphase properties on the interfacial conductivity and electrical conductivity of polymer nanocomposites

L_c is the minimum length of carbon nanotubes (CNTs) required for efficient transfer of filler conductivity to polymer matrix in polymer CNT nanocomposites (PCNTs). In this work, L_c is correlated with the dimensions of the CNTs and the interphase thickness. Subsequently, the interfacial conductivity as well as the effective length and concentration of CNTs are expressed by CNT and interphase properties. Moreover, a simple model for the tunneling conductivity of PCNTs is developed with these effective terms. The impacts of all parameters on L_c, the interfacial conductivity, the fraction of CNTs in the networks and the conductivity of the PCNT are explained and justified. In addition, the predictions of the percolation threshold and conductivity are compared with the experimental results of several samples. The desirable values of interfacial conductivity are achieved by thin, short and super‐conductive CNTs, high waviness and a thick interphase. However, thin and long CNTs, low waviness, a thick interphase, poor tunneling resistivity due to the polymer matrix and a short tunneling distance advantageously affect the conductivity of PCNTs, because they produce large conductive networks. The predictions also show good agreement with the experimental measurements of percolation threshold and conductivity, which confirms the developed equations. © 2020 Society of Chemical Industry     

Mutual influences of a chemical reaction and thermal radiation on a peristaltic pump of synovial nanofluids in a 3D tapered asymmetric channel

This investigation discusses the influences of a chemical reaction and concentration‐dependent viscosity on a magnetohydrodynamics peristaltic pump of synovial nanofluid in a tapered channel. Chemical reaction and Hall current effects are considered in the proposed investigation. The current study is solved for two suggestion models. In Model‐(I), the concentration is considered as a function in viscosity. In Model‐(II), concentration is considered as a function of the shear‐thinning index. The related study is rearranged under the models of low Reynolds number and long wavelength. The system study of highly nonlinear partial differential equations is explained mathematically with the aid of ParametricNDSolve by using Mathematica 11. Both models have been compared numerically and a huge difference is found between them. Results for velocity profile, temperature, and nanoparticle concentration distributions are obtained graphically for similar values of various physical parameters in three‐dimensional forms. Furthermore, a trapping bolus sketch is proposed in the terminus. The results confirm that the AJ patients can be cured by using the magnetic field in the presence of an electrically inducing influence, as a result of the effort of the ions inside the cell, which accelerates the metabolism of fluids. In addition, maximum values of velocity can control the friction between the joints and thus reduce arthritis.     

Effect of clad ratio on interfacial microstructure and properties of cladding billets via direct-chill casting process

Numerical simulation and experiments were introduced to develop AA4045/AA3003 cladding billets with different clad-ratios. The temperature fields, microstructures and mechanical properties near interface were investigated in detail. The results show that cladding billets with different clad-ratios were fabricated successfully. Si and Mn elements diffused across the bonding interface and formed diffusion layer. With the increase of clad-layer thickness, the interfacial region transforms from semisolid–solid state to liquid–solid state and the diffusion layer increased from 10 to 25 μm. The hardness at interface is higher than that of AA3003 side but lower than that of the other side. The bonding strength increased with the clad-layer thickness, attributing to solution strengthening due to elements diffusion. The cladding billets were extruded into clad pipe by indirect extrusion process after homogenization. The clad pipe remained the interfacial characteristics of as-cast cladding billet and the heredity of clad-ratio during deformation was testified.