The Effect of Titanium, Zirconium and Tin on the Growth of Diatom Synedra Acus and Morphology of Its Silica Valves

The effect of three Group IV metals (titanium, zirconium and tin) on the growth, morphology and chemical composition of the freshwater diatom Synedra acus subsp. radians (Kützing) Skabichevsky was studied and compared with germanium. The elements in their highest oxidation states were introduced into the culture medium in the form of hydroxides. Germanium was found to be toxic at ??5?mol. % of the total Ge-Si content in the culture medium. In the presence of other elements, a slight decrease in the cell division rate was observed independent of the element within 1?C15% content interval. The analysis of the obtained biomass and silica valves revealed the presence of all the added elements within the cells. However, only germanium was incorporated into the valves in considerable amounts. S. acus cultivation with the addition of 5% Group IV elements resulted in cells having the following aberrations in the structure of the silica valves: changes in valve shape, thickening of valves, alterations of the areolae rows, irregularity or absence of the areolae and a decrease in the mechanical strength of valves. Moreover, the effect of Group IV elements on silica formation was simulated in vitro using a synthetic polymer bearing polyamine and phosphate groups found in silaffines (proteins from diatom frustules). The studied elements were observed to provoke the formation of unstable silica particles in solution. We propose that the observed effects of germanium, titanium, zirconium and tin on diatom growth and structure are due to uncontrollable silica condensation.     

Charge Migration in Organic Materials: Can Propagating Charges Affect the Key Physical Quantities Controlling Their Motion?

Charge migration is a ubiquitous phenomenon with profound implications throughout many areas of chemistry, physics, biology, and materials science. The long-term vision of designing functional materials with tailored molecular-scale properties has triggered an increasing quest to identify prototypical systems where truly molecular conduction pathways play a fundamental role. Such pathways can be formed due to the molecular organization of various organic materials and are widely used to discuss electronic properties at the nanometer scale. Here, we present a computational methodology to study charge propagation in organic molecular stacks at nano and sub-nanoscales and exploit this methodology to demonstrate that moving charge carriers strongly affect the values of the physical quantities controlling their motion. The approach is also expected to find broad application in the field of charge migration in soft matter systems.     

Structure–properties investigations in hydrophilic nanocomposites based on polyurethane/poly(2–hydroxyethyl methacrylate) semi‐interpenetrating polymer networks and nanofiller densil for biomedical application

Nanocomposites based on sequential semi–interpenetrating polymer networks (semi–IPNs) of crosslinked polyurethane and linear poly(2‐hydroxyethyl methacrylate) filled with 1–15 wt % of nanofiller densil were prepared and investigated. Nanofiller densil used in an attempt to control the microphase separation of the polymer matrix by polymer–filler interactions. The morphology (SAXS, AFM), mechanical properties (stress–strain), thermal transitions (DSC) and polymer dynamics (DRS, TSDC) of the nanocomposites were investigated. Special attention has been paid to the raising of the hydration properties and the dynamics of water molecules in the nanocomposites in the perspective of biomedical applications. Nanoparticles were found to aggregate partially for higher than 3 and 5 wt % filler loading in semi–IPNs with 17 and 37 wt % PHEMA, respectively. The results show that the good hydration properties of the semi–IPN matrix are preserved in the nanocomposites, which in combination with results of thermal and dielectric techniques revealed also the existence of polymer–polymer and polymer–filler interactions. These interactions results also in the improvement of physical and mechanical properties of the nanocomposites in compare with the neat matrix. The improvement of mechanical properties in combination with hydrophilicity and biocompatibility of nanocomposites are promising for use these materials for biomedical application namely as surgical films for wound treatment and as material for producing the medical devises. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43122.     

Structure–property relationship of sodium deoxycholate based poly(ester ether)urethane ionomers for biomedical applications

New sodium deoxycholate based poly(ester ether)urethane ionomers were prepared for the development of biomedical materials. A structure–property relationship in the tested biomaterials was established by cross‐examination of the dynamic mechanical and dielectric properties, attenuated total reflection–Fourier transform infrared investigation, thermogravimetric analysis, and surface morphology characterization. A stronger ionic interaction and solvation capacity of the ions and a higher ionic conductivity were manifested in the case of poly(ethylene oxide)‐rich segments than for poly(propylene oxide)‐rich segments in these polyurethane ionomers. The molecular and ionic interactions of the bile‐salt moiety with different polyether cosoft segments influenced chain packing and conformation, supramolecular organization, and the resulting surface morphological microstructures of the polyurethane biomembranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42921.     

Introducing Glycolinkers for the Functionalization of Cytotoxic Drugs and Applications in Antibody–Drug Conjugation Chemistry

Antibody–drug conjugates (ADCs) are promising alternatives to naked antibodies for selective drug‐delivery applications and treatment of diseases such as cancer. Construction of ADCs relies upon site‐selective, efficient and mild conjugation technologies. The choice of a chemical linker is especially important, as it affects the overall properties of the ADC. We envisioned that hydrophilic bifunctional chemical linkers based on carbohydrates would be a useful class of derivatization agents for the construction of linker–drug conjugates and ADCs. Herein we describe the synthesis of carbohydrate‐based derivatization agents, glycolinker–drug conjugates featuring the tubulin inhibitor monomethyl auristatin E and an ADC based on an anti‐EGFR antibody. In addition, an initial in vitro cytotoxicity evaluation of the individual components and the ADC is provided against EGFR‐positive cancer cells.     

The Effect of La2O3 Addition on Sol–Gel Derived Mullitization

Monophasic gel with stoichiometric 3Al₂O₃·2SiO₂ composition and gels with 0.99, 1.96, and 2.91 mol% La₂O₃ added were sol–gel derived. The crystallization path, structure evolution, microstructure, and morphology of calcined premullite powders and sintered ceramic bodies have been investigated as a function of La₂O₃ content and sintering temperature. In addition to mullite, spinel phase at about 980°C, and α‐alumina at above 1000°C were determined; however, neither La₂O₃ nor La‐related compounds had crystallized. The La₂O₃ predominately incorporated into the glassy phase, enhanced with La₂O₃ level, which affected both mullite structure and composition, as confirmed by electron microscopy, Rietveld structure refinement, determination of unit cell parameters, electron microscopy, and achieved density of the sintered bodies. Increased thermal treatment changes the alumina/silica ratio in mullite (towards 3:2 below 1200°C, and toward 2:1 above), and decreases the mullite/amorphous ratio. Sintered dense ceramic bodies revealed a positive densification effect and increased sinterability as a result of the lanthanum‐induced increase in glassy phase.     

Preparation of polymeric nanocapsules via nano-sized poly(methoxydiethyleneglycol methacrylate) colloidal templates

Polymeric nanocapsules are attractive devices with a number of potential applications. In the present contribution we describe a method for nanocapsule preparation which is based on the formation of nanosized templates (mesoglobules, prepared from thermo-responsive poly(methoxydiethyleneglycol methacrylate)s, PDEGMA). These mesoglobules were coated with a cross-linked shell formed by pseudo-seeded radical polymerization of either N-isopropylacrylamide or 2-hydroxyethylmethacrylate in the presence of a cross-linking agent. Dissolution and removal of templates were achieved by extensive dialysis against water at temperatures below the LCST of PDEGMA. The obtained nanocapsules were visualized by transmission electron microscopy and their dimensions were determined by dynamic light scattering. The differences in the morphology of the nanocapsules were attributed to the different structures of the cross-linked membranes.     

Material properties and fire test results

Five material properties commonly used to describe the fire behavior of solids were evaluated as sole explanatory variables for four small‐scale fire tests with pass/fail outcomes by using a physically based probabilistic (phlogistic) burning model. The phlogistic model describes the likelihood of passing vertical Bunsen burner tests and a regulatory heat release rate test reasonably well over a wide range of material properties, as deduced from the correlation coefficient and mean deviation of the predicted and measured values. Of the thermal, combustion, and fire properties examined, the best predictors of the likelihood of passing the fire tests of this study were the heat of combustion of the sample, the heat release capacity, and the heat release parameter. The relative merits and drawbacks of qualitative (threshold) and quantitative (probabilistic) approaches to predicting fire test results using thermal and combustion properties are discussed. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Upregulation of Cathepsin X in Glioblastoma: Interplay with γ-Enolase and the Effects of Selective Cathepsin X Inhibitors

Glioblastoma (GBM) is the most common and deadly primary brain tumor in adults. Understanding GBM pathobiology and discovering novel therapeutic targets are critical to finding efficient treatments. Upregulation of the lysosomal cysteine carboxypeptidase cathepsin X has been linked to immune dysfunction and neurodegenerative diseases, but its role in cancer and particularly in GBM progression in patients is unknown. In this study, cathepsin X expression and activity were found to be upregulated in human GBM tissues compared to low-grade gliomas and nontumor brain tissues. Cathepsin X was localized in GBM cells as well as in tumor-associated macrophages and microglia. Subsequently, potent irreversible (AMS36) and reversible (Z7) selective cathepsin X inhibitors were tested in vitro. Selective cathepsin X inhibitors decreased the viability of patient-derived GBM cells as well as macrophages and microglia that were cultured in conditioned media of GBM cells. We next examined the expression pattern of neuron-specific enzyme γ-enolase, which is the target of cathepsin X. We found that there was a correlation between high proteolytic activity of cathepsin X and C-terminal cleavage of γ-enolase and that cathepsin X and γ-enolase were colocalized in GBM tissues, preferentially in GBM-associated macrophages and microglia. Taken together, our results on patient-derived material suggest that cathepsin X is involved in GBM progression and is a potential target for therapeutic approaches against GBM.