Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

Prediction of mode I fracture toughness of rock using linear multiple regression and gene expression programming

Prediction of mode I fracture toughness (K_IC) of rock is of significant importance in rock engineering analyses. In this study, linear multiple regression (LMR) and gene expression programming (GEP) methods were used to provide a reliable relationship to determine mode I fracture toughness of rock. The presented model was developed based on 60 datasets taken from the previous literature. To predict fracture parameters, three mechanical parameters of rock mass including uniaxial compressive strength (UCS), Brazilian tensile strength (BTS), and elastic modulus (E) have been selected as the input parameters. A cluster of data was collected and divided into two random groups of training and testing datasets. Then, different statistical linear and artificial intelligence based nonlinear analyses were conducted on the training data to provide a reliable prediction model of K_IC. These two predictive methods were then evaluated based on the testing data. To evaluate the efficiency of the proposed models for predicting the mode I fracture toughness of rock, various statistical indices including coefficient of determination (R²), root mean square error (RMSE), and mean absolute error (MAE) were utilized herein. In the case of testing datasets, the values of R², RMSE, and MAE for the GEP model were 0.87, 0.188, and 0.156, respectively, while they were 0.74, 0.473, and 0.223, respectively, for the LMR model. The results indicated that the selected GEP model delivered superior performance with a higher R² value and lower errors.     

Adaptation to Endoplasmic Reticulum Stress Enhances Resistance of Oral Cancer Cells to Cisplatin by Up-Regulating Polymerase η and Increasing DNA Repair Efficiency

Endoplasmic reticulum (ER) stress response is an adaptive program to cope with cellular stress that disturbs the function and homeostasis of ER, which commonly occurs during cancer progression to late stage. Late-stage cancers, mostly requiring chemotherapy, often develop treatment resistance. Chemoresistance has been linked to ER stress response; however, most of the evidence has come from studies that correlate the expression of stress markers with poor prognosis or demonstrate proapoptosis by the knockdown of stress-responsive genes. Since ER stress in cancers usually persists and is essentially not induced by genetic manipulations, we used low doses of ER stress inducers at levels that allowed cell adaptation to occur in order to investigate the effect of stress response on chemoresistance. We found that prolonged tolerable ER stress promotes mesenchymal–epithelial transition, slows cell-cycle progression, and delays the S-phase exit. Consequently, cisplatin-induced apoptosis was significantly decreased in stress-adapted cells, implying their acquisition of cisplatin resistance. Molecularly, we found that proliferating cell nuclear antigen (PCNA) ubiquitination and the expression of polymerase η, the main polymerase responsible for translesion synthesis across cisplatin-DNA damage, were up-regulated in ER stress-adaptive cells, and their enhanced cisplatin resistance was abrogated by the knockout of polymerase η. We also found that a fraction of p53 in stress-adapted cells was translocated to the nucleus, and that these cells exhibited a significant decline in the level of cisplatin-DNA damage. Consistently, we showed that the nuclear p53 coincided with strong positivity of glucose-related protein 78 (GRP78) on immunostaining of clinical biopsies, and the cisplatin-based chemotherapy was less effective for patients with high levels of ER stress. Taken together, this study uncovers that adaptation to ER stress enhances DNA repair and damage tolerance, with which stressed cells gain resistance to chemotherapeutics.     

Extracellular Vesicles and Asthma—More Than Just a Co-Existence

Extracellular vesicles (EVs) are membranous structures, which are secreted by almost every cell type analyzed so far. In addition to their importance for cell-cell communication under physiological conditions, EVs are also released during pathogenesis and mechanistically contribute to this process. Here we summarize their functional relevance in asthma, one of the most common chronic non-communicable diseases. Asthma is a complex persistent inflammatory disorder of the airways characterized by reversible airflow obstruction and, from a long-term perspective, airway remodeling. Overall, mechanistic studies summarized here indicate the importance of different subtypes of EVs and their variable cargoes in the functioning of the pathways underlying asthma, and show some interesting potential for the development of future therapeutic interventions. Association studies in turn demonstrate a good diagnostic potential of EVs in asthma.     

Phosphorylated chitosan/poly(vinyl alcohol) based proton exchange membranes modified with propylammonium nitrate ionic liquid and silica filler for fuel cell applications

In our previous work, phosphorylated chitosan was modified through polymer blending with poly(vinyl alcohol) (PVA) polymer to produce N-methylene phosphonic chitosan/poly(vinyl alcohol) (NMPC/PVA) composite membranes. The aim of this work is to further investigate the effects of a propylammonium nitrate (PAN) ionic liquid and/or silicon dioxide (SiO₂) filler on the morphology and physical properties of NMPC/PVA composite membranes. The temperature-dependent ionic conductivity of the composite membranes with various ionic liquid and filler compositions was studied by varying the loading of PAN ionic liquid and SiO₂-PAN filler in the range of 5–20 wt%. As the loading of PAN ionic liquid increased in the NMPC/PVA membrane matrix, the ionic conductivity value also increased with the highest value of 0.53 × 10^?3 S cm^?1 at 25 °C and increased to 1.54 × 10^?3 S cm^?1 at 100 °C with 20 wt% PAN. The NMPC/PVA-PAN (20 wt%) composite membrane also exhibited the highest water uptake and ion exchange capacity, with values of 60.5% and 0.60 mequiv g^?1, respectively. In addition, in the single-cell performance test, the NMPC/PVA-PAN (20 wt%) composite membrane displayed a maximum power density, which was increased by approximately 14% compared to the NMPC/PVA composite membrane with 5 wt% SiO₂-PAN. This work demonstrated that modified NMPC/PVA composite membranes with ionic liquid PAN and/or SiO₂ filler showed enhanced performance compared with unmodified NMPC/PVA composite membranes for proton exchange membrane fuel cells.     

Chemoenzymatic Asymmetric Synthesis of Pyridine-Based α-Fluorinated Secondary Alcohols

Fluoro-substituted and heteroaromatic compounds are valuable intermediates for a variety of applications in pharma- and agrochemistry and synthetic chemistry. This study investigates the chemoenzymatic preparation of chiral alcohols bearing a heteroaromatic ring with an increasing degree of fluorination in α-position. Starting from readily available picoline derivatives prochiral α-halogenated acyl moieties were introduced with excellent selectivity and 64–95 % yield. The formed carbonyl group was subsequently reduced to the corresponding alcohols using the alcohol dehydrogenase from Lactobacillus kefir, yielding an enantiomeric excess of 95–>99 % and up to 98 % yield.     

Blends of Bio-Based Poly(Limonene Carbonate) with Commodity Polymers

In this study, blends of the bio-based poly(limonene carbonate) (PLimC) with different commodity polymers are investigated in order to explore the potential of PLimC toward generating more sustainable polymer materials by reducing the amount of petro- or food-based polymers. PLimC is employed as minority component in the blends. Next to the morphology and thermal properties of the blends the impact of PLimC on the mechanical properties of the matrix polymers is studied. The interplay of incompatibility and zero-shear melt viscosity contrast determines the blend morphology, leading for all blends to a dispersed droplet morphology for PLimC. Blends with polymers of similar structure to PLimC (i.e., aliphatic/aromatic polyester) show the best performance with respect to mechanical properties, whereas blends with polystyrene or poly(methyl methacrylate) are too brittle and polyamide 12 blends show very low elongations at break. In blends with Ecoflex (poly(butylene adipate-co-terephthalate)) and Arnitel EM400 (copoly(ether ester)) with poly(butylene terephthalate) hard and polytetrahydrofuran soft segments) a threefold increase in E-modulus can be achieved, while keeping the elongation at break at reasonable high values of ≈200%, making these blends highly interesting for applications.     

Revealing the high sensitivity in the metal toinsulator transition properties of the pulsed laser deposited VO2 thin films

Vanadium dioxide (VO₂) is known as a typical 3d-orbital transition metal oxide exhibiting the metal-to-insulator-transition (MIT) property near room temperature. However, their electronic applications have been challenged by the quality and uniformity of VO₂ thin films. In this work, we demonstrate the high sensitivity in the valence charge of vanadium and the MIT properties of the VO₂ thin films to the deposition temperature. This observation indicates the necessity to eliminate the inhomogeneity in the temperature distribution of substrate during the vacuum-deposition process of VO₂. In addition, a high thermoelectric power factor (PF, e.g., exceeding 1 μWcm⁻¹K⁻²) was achieved in the metallic phase of the VO₂ thin films and this value is comparable to typical organic or oxide thermoelectric materials. We believe this high PF enriches the potential functionality in thermoelectric energy conversions beyond the existing electronic applications of the current vacuum-grown VO₂ thin films.     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.