Torrefied biomass‐polypropylene composites

Torrefied almond shells and wood chips were incorporated into polypropylene as fillers to produce torrefied biomass‐polymer composites. The composites were prepared by extrusion and injection molding. Response surface methodology was used to examine the effects of filler concentration, filler size, and lignin factor (relative lignin to cellulose concentration) on the material properties of the composites. The heat distortion temperatures, thermal properties, and tensile properties of the composites were characterized by thermomechanical analysis, differential scanning calorimetry, and tensile tests, respectively. The torrefied biomass composites had heat distortion temperatures of 8–24°C higher than that of neat polypropylene. This was due to the torrefied biomass restricting mobility of polypropylene chains, leading to higher temperatures for deformation. The incorporation of torrefied biomass generally resulted in an increase in glass transition temperature, but did not affect melting temperature. Also, the composites had lower tensile strength and elongation at break values than those of neat polypropylene, indicating weak adhesion between torrefied biomass and polypropylene. However, scanning electron microscopy results did indicate some adhesion between torrefied biomass and polypropylene. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41582.     

Design of an Ultrafast G Protein Switch Based on a Mouse Melanopsin Variant

The primary goal of optogenetics is the light-controlled noninvasive and specific manipulation of various cellular processes. Herein, we present a hybrid strategy for targeted protein engineering combining computational techniques with electrophysiological and UV/visible spectroscopic experiments. We validated our concept for channelrhodopsin-2 and applied it to modify the less-well-studied vertebrate opsin melanopsin. Melanopsin is a promising optogenetic tool that functions as a selective molecular light switch for G protein-coupled receptor pathways. Thus, we constructed a model of the melanopsin G_q protein complex and predicted an absorption maximum shift of the Y211F variant. This variant displays a narrow blue-shifted action spectrum and twofold faster deactivation kinetics compared to wild-type melanopsin on G protein-coupled inward rectifying K⁺ (GIRK) channels in HEK293 cells. Furthermore, we verified the in vivo activity and optogenetic potential for the variant in mice. Thus, we propose that our developed concept will be generally applicable to designing optogenetic tools.     

Metastatic cancer cell attachment to endothelium is promoted by endothelial glycocalyx sialic acid degradation

While it is known that cancer cell interactions with vascular endothelial cells (ECs) drive metastatic cancer cell extravasation from blood vessels into secondary tumor sites, the mechanisms of action are still poorly understood. Here, we tested the hypothesis that neuraminidase-induced degradation of EC surface glycocalyx (GCX), particularly the sialic acid (SA) residue components of the GCX, will substantially increase metastatic cancer cell attachment to ECs. To our knowledge, our study is the first to isolate the role of GCX SA residues in cancer cell attachment to the endothelium, which were found to be differentially affected by the presence of neuraminidase and to indeed regulate metastatic cancer cell homing to ECs. We hope that this work will eventually translate to identification of EC GCX-based cancer markers that can be therapeutically targeted to hinder the progression of metastasis.     

Lipids from Wastewater-Activated Sludge Cultivated on Acetic Acid as Potential Alternatives to High-Value Oils and Fats

This study focuses on new interpretations of the published literature by statistically evaluating the potential of microbial lipids from activated sludge (AS) as alternatives to high-value oils and fats. There are two data analysis stages involved in this study after compilation and organization of fatty acid profiles from the literature databases: (1) comparison of fatty acid profiles of the cultivated AS lipids with that of oils and fats found in the literature databases, and (2) hierarchical cluster analysis of the fatty acids of the combined dataset of literature oils and fats, and the AS lipids. Results show that fatty acid profiles of lipids from cultivated AS were similar to the fatty acid profiles of some oils and fats of plant, animal, single-microbial cultures, and algal origins; hence, lipids from AS could be potential alternatives to specialty oils and fats. The cultivation conditions of AS during lipid content enhancement may influence lipid application.     

Amidoamine: Synthesis,disparity in cure with epoxy resins between bulk and solvent systems,and structure–property relationships of its epoxy‐based coatings

Amidoamines are widely used as crosslinkers for epoxy resins in protective coatings on metal substrates; however, their cure chemistry is not well elaborated in the technical literature. During cure, the epoxy–amine and epoxy–amide NH reactions could be accompanied by epoxy–hydroxyl etherification, epoxy–epoxy homopolymerization, and reaction between hydroxyls and amide moiety to form in situ ester and amine. To understand the epoxy–amidoamine cure chemistry and correlate it with coating performance properties, amidoamines of known structure are required. Therefore, amidoamines were synthesized by reacting dimer fatty acids with diethylene triamine. When these amidoamines were cured with epoxy resins, discrepancies were observed between systems cured at ambient and thermal conditions. The presence of solvents were seen to greatly affect the rate of epoxy–amidoamine cure at ambient, and before and after vitrification. Near‐IR and mid‐IR spectroscopy studies indicated that side reactions occurred to some extent during cure. No reaction was noted between the amide NH moiety and the epoxide group below 150°C whereas ester formation was noted above 120°C. Solvent‐based clear epoxy–amidoamine coatings formulated at an epoxy:amine equivalent ratio 1.15 passed basic organic coatings evaluation tests. POLYM. ENG. SCI., 59:E69–E81, 2019. © 2018 Society of Plastics Engineers     

Raft crystals of poly(isoprene)-block-poly(ferrocenyldimethylsilane) and their surface wetting behavior during melting as observed by AFM and NanoTA

We report on the morphology evolution during heating and melting of lamellar poly(isoprene)-block-poly(ferrocenyldimethylsilane) (PI₇₆-b-PFDMS₇₆) raft crystals deposited at the native oxide surface of silicon (SiO₂) or at a highly ordered pyrolytic graphite (HOPG) surface, studied by in situ temperature controlled atomic force microscopy. Crystals deposited on hydrophilic SiO₂ surfaces revealed an irreversible decrease in length at temperatures of up to tens of degrees above their expected melting temperature, while maintaining their platelet-like structure. Crystals deposited on hydrophobic HOPG surfaces initially decreased in length below their expected melting temperature, while at 120 °C and above a typical molten morphology was observed. In addition, the irreversible formation of a PI₇₆-b-PFDMS₇₆ wetting layer around the crystals was observed upon increasing the temperature. These observations in the morphological behavior upon heating emphasize the role of interfacial energy between a surface deposited block copolymer based macromolecular nanostructure and its supporting substrate.     

Fabrication of oriented electrospun cellulose nanocrystals–polystyrene composite fibers on a rotating drum

Nitrobenzene (CNC-1), trifluoromethyl benzene (CNC-2) modified and polystyrene-grafted (CNC-g) cellulose nanocrystals in polystyrene (PS)-N,N dimethylformamide (DMF) solutions were electrospun and collected as stretched and aligned fibers on a rotating drum. Scanning electron microscope pictures showed significant alignment in the case of unmodified and nitrobenzene-modified CNC-1/PS nanocomposite fibers once the linear speed of rotor reached to 15 m s⁻¹. Fiber diameter decrease was more strong with rotor speed increase in the case of trifluoromethyl benzene modified (CNC-2) and polystyrene-grafted (CNC-g) cellulose nanocrystals/PS systems. Dynamic mechanical analysis including storage and elastic modulus of electrospun-oriented fibers were performed on surface-modified and polymer-grafted CNC/PS samples. According to α transition peak, the increase in the glass-transition temperature with filler concentration was the highest in polymer-grafted CNC-g/PS composite fibers. It was due to the interpenetration of grafted polymer brushes and free polymer chains in continuous phase and resulted in restrictions of motions of polymer chains in the PS matrix. The elastic moduli of nitrobenzene (CNC-1) and trifluoromethyl benzene (CNC-2)-modified CNC-filled PS composite fibers agreed well with percolation model, which indicates the CNC–CNC interactions and network formation with an increase in concentration. Magnitude of the elastic modulus of polymer grafted CNC-g at 0.33 vol % in PS was significantly higher than the prediction from percolation theory. It was due the immobilized polymer chains around CNC-g particles. However, grafted polymer chains, at higher CNC concentrations acted like stickers among CNC particles and caused CNC agglomerates with entrapped free polystyrene from the matrix, thus caused a decrease in the elastic modulus. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48942.     

In Silico/In Vitro Hit-to-Lead Methodology Yields SMYD3 Inhibitor That Eliminates Unrestrained Proliferation of Breast Carcinoma Cells

SMYD3 is a lysine methyltransferase that regulates the expression of over 80 genes and is required for the uncontrolled proliferation of most breast, colorectal, and hepatocellular carcinomas. The elimination of SMYD3 restores normal expression patterns of these genes and halts aberrant cell proliferation, making it a promising target for small molecule inhibition. In this study, we sought to establish a proof of concept for our in silico/in vitro hit-to-lead enzyme inhibitor development platform and to identify a lead small molecule candidate for SMYD3 inhibition. We used Schrodinger^® software to screen libraries of small molecules in silico and the five compounds with the greatest predicted binding affinity within the SMYD3 binding pocket were purchased and assessed in vitro in direct binding assays and in breast cancer cell lines. We have confirmed the ability of one of these inhibitors, Inhibitor-4, to restore normal rates of cell proliferation, arrest the cell cycle, and induce apoptosis in breast cancer cells without affecting wildtype cell behavior. Our results provide a proof of concept for this fast and affordable small molecule hit-to-lead methodology as well as a promising candidate small molecule SMYD3 inhibitor for the treatment of human cancer.     

Direct writing of textured ceramics using anisotropic nozzles

Direct writing is a unique means to align anisotropic particles for the fabrication of textured ceramics by templated grain growth (TGG). We show that alignment of tabular barium titanate (BT) template particles (20–40 μm width and 0.5–2 μm thickness) in a PIN-PMN-PT matrix powder (d₅₀ = 280 nm) is significantly improved during direct writing using anisotropic nozzles at high printing rates. The particle orientation distribution in as-printed filaments, and the texture orientation distribution in sintered ceramic filaments are shown to directly correlate with COMSOL Multiphysics-predicted torque distributions for direct writing with aspect ratio 2, 3 and 5 oval nozzles. Electromechanical strain properties of the textured piezoelectric ceramics significantly improved relative to random ceramics when printed with anisotropic nozzles. Simulations of aspect ratio 20 nozzles and nozzles with interior baffles demonstrate significantly increased torque and near elimination of constant shear stress cores (i.e. plug flow).