Phytochrome‐Based Extracellular Matrix with Reversibly Tunable Mechanical Properties

Interrogation and control of cellular fate and function using optogenetics is providing revolutionary insights into biology. Optogenetic control of cells is achieved by coupling genetically encoded photoreceptors to cellular effectors and enables unprecedented spatiotemporal control of signaling processes. Here, a fast and reversibly switchable photoreceptor is used to tune the mechanical properties of polymer materials in a fully reversible, wavelength‐specific, and dose‐ and space‐controlled manner. By integrating engineered cyanobacterial phytochrome 1 into a poly(ethylene glycol) matrix, hydrogel materials responsive to light in the cell‐compatible red/far‐red spectrum are synthesized. These materials are applied to study in human mesenchymal stem cells how different mechanosignaling pathways respond to changing mechanical environments and to control the migration of primary immune cells in 3D. This optogenetics‐inspired matrix allows fundamental questions of how cells react to dynamic mechanical environments to be addressed. Further, remote control of such matrices can create new opportunities for tissue engineering or provide a basis for optically stimulated drug depots.     

Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich Oxides

Deciphering the sophisticated interplay between thermodynamics and kinetics of high-temperature lithiation reaction is fundamentally significant for designing and preparing cathode materials. Here, the formation pathway of Ni-rich layered ordered LiNi_0.6Co_0.2Mn_0.2O₂ (O-LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequilibrium phase transition from the reactants to a metastable disordered Li_1−x(Ni_0.6Co_0.2Mn_0.2)_1+xO₂ (D-LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equilibrium phase (O-LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D-LNCM622O is well-fitted to a model of first-order disorder-to-order transition. The long-range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady-state as a function of heating time at selected temperatures. The dominant kinetic pathways revealed here will be instrumental in achieving high-performance cathode materials. Importantly, the O-LNCM622O tends to form the D-LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long-range cationic (dis)ordering in the Ni-rich cathodes could affect the structural evolution during cycling and thus their electrochemical properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.     

Organic Single Crystal Patterning Method for Micrometric Photosensors

Light detection technologies are of interest due to their applications in energy conversion and optical communications. Single-crystal organic semiconductors, such as rubrene, present high detectivities and charge carrier mobility, making them attractive for light-sensing applications. Growth of high crystallinity organic crystals is achieved using vapor processes, forming crystals of arbitrary shapes and orientations and requiring posterior patterning processes. However, patterning the organic semiconductors using industry-standard microfabrication techniques is not straightforward, as these often cause irreversible damage to the crystals. Here the fabrication of patterned micrometric rubrene photosensors is demonstrated through a combination of photolithography and Reactive Ion Etching steps. Protective layers during microfabrication minimize degradation of optoelectronic properties of the organic single crystals during fabrication. Crystals undergoing the patterning process presented a survival rate of 39%. Photoresponse values of up to 41 mA W⁻¹ are obtained under illumination at 500 nm. This opens a route for the industrial-scale fabrication process of high-performance optoelectronic devices based on organic crystals semiconductors.     

Inhibitory effect of boldine on fish oil oxidation

The antioxidative effect of boldine, an alkaloid extracted fromPeumus boldus Mol. (boldo), was assayed on the spontaneous and on the metal-induced oxidation of fish oil. The inhibitory effect of boldine was compared to those of dl-α tocopherol, the flavonoid quercetin and the synthetic antioxidants butylated hydroxytoluene and butylated hydroxyanisole. Boldine, in all assays, showed a good antioxidative effect, which was comparable to that of quercetin and even better than that of dl-α tocopherol and the synthetic antioxidants. Additive effects were observed when mixtures of boldine and quercetin or dl-α tocopherol were assayed. The present study supports the potential use of boldine as a novel natural antioxidant for fish oil.     

Mesoscopic structure and swelling properties of crosslinked polyethylene glycol in water

In this paper, we present our efforts in modeling and simulation of polyethylene glycol crosslinked with an isocyanate tHDI. The polymer, by its nature, is hydrophilic and has strong hydrogen bond interactions with water. The simulations are performed at coarse-grained scale by using a dissipative particle dynamics (DPD) simulation method. The effect of hydrogen bond between water and polymer beads on the structure of the crosslinked hydrophilic polymer structure is studied. The polymer is observed to phase separate with water in the absence of hydrogen bonds in DPD simulations. In the reverse case, where hydrogen bonds are explicitly included in DPD simulations, polymer mixes with water. This behavior is investigated by plotting the density profiles. Moreover, the volumetric swelling behavior in mixtures with different water contents is estimated from simulations and extrapolated by a polynomial fit to compare with experiments. It is observed that the predicted swelling ratio is in good agreement with the experimental measurements.     

Forest‐based resources as fillers in biobased polyurethane foams

Six fillers from forestry wastes (wood, bark, cones and needles from young pine trees, kraft lignin, and recycled paper sludge from industry wastes) were incorporated into polyurethane (PU)‐based foams prepared via free‐rise pouring method. Variable filler contents (1, 5, and 10 wt %) and NCO/OH ratios (0.6, 0.9, and 1.2) were investigated. A simple mixture (1:3) of castor oil and crude glycerin (byproduct from biodiesel production) was used as biobased polyol. The foam composites were investigated through spectroscopy, morphological, mechanical, and hygroscopic analyses. The addition of fillers decreased water uptake and yielded rigid PU systems with more homogenous cell structure. The 1% and 5% reinforcement wood were the most effective among the studied compositions, with better mechanical and hygroscopic performance, probably due the higher compatibility of the wood with the PU system, which promote urethanic bonds between filler and isocyanate, as indicated by wet chemical results and micrographs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45684.     

Self‐aggregated nanoparticles of N‐dodecyl,N′‐glycidyl(chitosan) as pH‐responsive drug delivery systems for quercetin

In this study, pH‐responsive amphiphilic chitosan (CS) nanoparticles were used to encapsulate quercetin (QCT) for sustained release in cancer therapy. The novel CS derivatives were obtained by synthesis with 2,3‐epoxy‐1‐propanol, also known as glycidol, followed by acylation with dodecyl aldehyde. Characterization was performed by spectroscopic, viscosimetric, and size‐determination methods. Critical aggregation concentration, morphology, entrapment efficiency, drug release profile, cytotoxicity, and hemocompatibility studies were also carried out. The average size distribution of the self‐assembling nanoparticles measured by dynamic light scattering ranged from 140 to 300 nm. In vitro QCT release and Korsmeyer–Peppas model indicated that pH had a major role in drug release. Cytotoxicity assessments indicated that the nanoparticles were non‐cytotoxic. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay further revealed that QCT‐loaded nanoparticles could inhibit MCF‐7 cell growth. In vitro erythrocyte‐induced hemolysis indicated the good hemocompatibility of the nanoparticles. These results suggest that the synthesized copolymers might be potential carriers for hydrophobic drugs in cancer therapy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45678.     

Industrial effluents and surface waters genotoxicity and mutagenicity evaluation of a river of Tucuman, Argentina

Assessment of water pollution and its effect upon river biotic communities and human health is indispensable to develop control and management strategies. The aim of this work was to ascertain the biotoxicity of water pollution in samples from industrial effluent discharge areas of Tucumán, Argentina by means of biological tests. Chemical characterization of the water pollution was verified by measuring dissolved oxygen concentration or levels of suspended matter and salts. Genotoxic/mutagenic potential was determined using Allium anaphase-telophase and Ames/Salmonella tests. All samples were phytotoxic and genotoxic for Allium roots. Micronucleus and anaphase aberrations were observed, but they did not show mutagenic effects on Salmonella typhimurium, TA98 and TA100 strains with and without metabolic activation (S9). Our results show the importance of testing industrial effluents by chemical methods and complementary biological tests to optimize the control policy on these environmental samples.     

Assessing methods for blood cell cytotoxic responses to inorganic nanoparticles and nanoparticle aggregates

Inorganic nanoparticles (NPs) show great potential for medicinal therapy. However, biocompatibility studies are essential to determine if they are safe. Here, five different NPs are compared for their cytotoxicity, internalization, aggregation in medium, and reactive oxygen species (ROS) production, using tumoral and normal human blood cells. Differences depending on the cell type are analyzed, and no direct correlation between ROS production and cell toxicity is found. Results are discussed with the aim of standardizing the procedures for the evaluation of the toxicity.