Refractory Alkali-Free Cristobalite Glass-Ceramics: Activated Reaction Sinter-Crystallization Synthesis and Properties

A new approach for the synthesis of chemically stabilized β-cristobalite-like glass-ceramic materials is developed. It is based on an activated reaction sinter-crystallization process of compacted powder mixtures at relatively low temperatures (1400–1450°C) and short heat treatment times. To facilitate homogeneous dopant distribution and thus the formation of a high content of β_x-cristobalite-like phases, possessing a very low thermal expansion coefficient, the batch components are introduced in a chemically, mechanically, or thermally preactivated form. In this way, the high-temperature glass premelting usually employed in the “classical” synthesis of glass-ceramics is avoided. Using different, mutually complementary techniques of analysis it is revealed that optimal refractory properties are achieved with glass-ceramics containing α_x- and β_x-cristobalite solid solutions with close values of the lattice parameters. In this case, the transformation between these two cristobalite-like solid solutions proceeds instead by a first-order displacive transition, by a process exhibiting features characteristic for both a suppressed first-order phase change and a second-order λ-type phase transitions. The refractory properties of the glass-ceramic materials thus synthesized and the possibility to use various forming techniques open many fields for their application.     

Fluidization of spherical versus elongated particles: Experimental investigation using magnetic particle tracking

In biomass processing fluidized beds are used to process granular materials where particles typically possess elongated shapes. However, for simplicity, in computer simulations particles are often considered spherical, even though elongated particles experience more complex particle– particle interactions as well as different hydrodynamic forces. The exact effect of these more complex interactions in dense fluidized suspensions is still not well understood. In this study we use the magnetic particle tracking technique to compare the fluidization behavior of spherical particles to that of elongated particles. We found a considerable difference between fluidization behavior of spherical versus elongated particles in the time-averaged particle velocity field as well as in the time-averaged particle rotational velocity profile. Moreover, we studied the effect of fluid velocity and the particle's aspect ratio on the particle's preferred orientation in different parts of the bed, which provides new insight in the fluidization behavior of elongated particles.     

Multiple Chemical Features Impact Biological Performance Diversity of a Highly Active Natural Product-Inspired Library

A systematic, diversity-oriented synthesis approach was employed to access a natural product-inspired flavonoid library with diverse chemical features, including chemical properties, scaffold, stereochemistry, and appendages. Using Cell Painting, the effects of these diversity elements were evaluated, and multiple chemical features that predict biological performance diversity were identified. Scaffold identity appears to be the dominant predictor of performance diversity, but stereochemistry and appendages also contribute to a lesser degree. In addition, the diversity of chemical properties contributed to performance diversity, and the driving chemical property was dependent on the scaffold. These results highlight the importance of key chemical features that may inform the creation of small-molecule, performance-diverse libraries to improve the efficiency and success of high-throughput screening campaigns.     

Manipulation of Chemically Mediated Interactions in Agricultural Soils to Enhance the Control of Crop Pests and to Improve Crop Yield

In most agro-ecosystems the organisms that feed on plant roots have an important impact on crop yield and can impose tremendous costs to farmers. Similar to aboveground pests, they rely on a broad range of chemical cues to locate their host plant. In their turn, plants have co-evolved a large arsenal of direct and indirect defense to face these attacks. For instance, insect herbivory induces the synthesis and release of specific volatile compounds in plants. These volatiles have been shown to be highly attractive to natural enemies of the herbivores, such as parasitoids, predators, or entomopathogenic nematodes. So far few of the key compounds mediating these so-called tritrophic interactions have been identified and only few genes and biochemical pathways responsible for the production of the emitted volatiles have been elucidated and described. Roots also exude chemicals that directly impact belowground herbivores by altering their behavior or development. Many of these compounds remain unknown, but the identification of, for instance, a key compound that triggers nematode egg hatching to some plant parasitic nematodes has great potential for application in crop protection. These advances in understanding the chemical emissions and their role in ecological signaling open novel ways to manipulate plant exudates in order to enhance their natural defense properties. The potential of this approach is discussed, and we identify several gaps in our knowledge and steps that need to be taken to arrive at ecologically sound strategies for belowground pest management.     

Reorganization of perylene bisimide J-aggregates: from delocalized collective to localized individual excitations

Water-induced reorganization of individual one-dimensional J-aggregates of perylene bisimide (PBI) dyes was observed by fluorescence microscopy. Fluorescence spectra and decay kinetics of individual J-aggregates immobilized on glass surfaces were measured under a dry nitrogen atmosphere and under humid conditions. The fluorescence properties of PBI J-aggregates arisen from collective excitons under dry nitrogen atmosphere were changed to those of non-interacting dye monomers when water vapor was introduced into the environment (sample chamber). Time-dependent changes of the fluorescence spectra and lifetimes upon exposure to water vapor suggest an initial coordination of water molecules at defect sites leading to the formation of H-type dimer units that act as exciton quenchers, and a subsequent slower disintegration of the hydrogen-bonded J-aggregate into monomers that lack resonance coupling. Our present studies resulted in a direct demonstration of how drastically the optical properties of molecular ensembles and characteristics of their excited states can be changed by delicate reorganization of dye molecules at nanometre scales.     

Metabolism of Storage Lipids and the Role of Lipid Droplets in the Yeast Schizosaccharomyces pombe

Storage lipids, triacylglycerols (TAG), and steryl esters (SE), are predominant constituents of lipid droplets (LD) in fungi. In several yeast species, metabolism of TAG and SE is linked to various cellular processes, including cell division, sporulation, apoptosis, response to stress, and lipotoxicity. In addition, TAG are an important source for the generation of value-added lipids for industrial and biomedical applications. The fission yeast Schizosaccharomyces pombe is a widely used unicellular eukaryotic model organism. It is a powerful tractable system used to study various aspects of eukaryotic cellular and molecular biology. However, the knowledge of S. pombe neutral lipids metabolism is quite limited. In this review, we summarize and discuss the current knowledge of the homeostasis of storage lipids and of the role of LD in the fission yeast S. pombe with the aim to stimulate research of lipid metabolism and its connection with other essential cellular processes. We also discuss the advantages and disadvantages of fission yeast in lipid biotechnology and recent achievements in the use of S. pombe in the biotechnological production of valuable lipid compounds.     

Synthetic Peroxides Promote Apoptosis of Cancer Cells by Inhibiting P-Glycoprotein ABCB5

This article discloses a new horizon for the application of peroxides in medical chemistry. Stable cyclic peroxides are demonstrated to have cytotoxic activity against cancer cells; in addition a mechanism of cytotoxic action is proposed. Synthetic bridged 1,2,4,5-tetraoxanes and ozonides were effective against HepG2 cancer cells and some ozonides selectively targeted liver cancer cells (the selectivity indexes for compounds 11 b and 12 a are 8 and 5, respectively). In some cases, tetraoxanes and ozonides were more selective than paclitaxel, artemisinin, and artesunic acid. Annexin V flow-cytometry analysis revealed that the active ozonides 22 a and 23 a induced cell death of HepG2 by apoptosis. Further study showed that compounds 22 a and 23 a exhibited a strong inhibitory effect on P-glycoprotein (P-gp/ABCB5)-overexpressing HepG2 cancer cells. ABCB5 is a key player in the multidrug-resistant phenotype of liver cancer. Peroxides failed to demonstrate a direct correlation between oxidative potential and their biological activity. To our knowledge this is the first time that peroxide diastereoisomers have been found to show stereospecific antimalarial action against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Stereoisomeric ozonide 12 b is 11 times more active than stereoisomeric ozonide 12 a (IC₅₀=5.81 vs 65.18 μm ). Current findings mean that ozonides merit further investigation as potential therapeutic agents for drug-resistant hepatocellular carcinoma.     

Imaging of KCa3.1 Channels in Tumor Cells with PET and Small-Molecule Fluorescent Probes

The Ca²⁺ activated K⁺ channel K_Ca3.1 is overexpressed in several human tumor cell lines, e. g. clear cell renal carcinoma, prostate cancer, non-small cell lung cancer. Highly aggressive cancer cells use this ion channel for key processes of the metastatic cascade such as migration, extravasation and invasion. Therefore, small molecules, which are able to image this K_Ca3.1 channel in vitro and in vivo represent valuable diagnostic and prognostic tool compounds. The [¹⁸F]fluoroethyltriazolyl substituted senicapoc was used as positron emission tomography (PET) tracer and showed promising properties for imaging of K_Ca3.1 channels in lung adenocarcinoma cells in mice. The novel senicapoc BODIPY conjugates with two F-atoms ( 9 a ) and with a F-atom and a methoxy moiety ( 9 b ) at the B-atom led to the characteristic punctate staining pattern resulting from labeling of single K_Ca3.1 channels in A549-3R cells. This punctate pattern was completely removed by preincubation with an excess of senicapoc confirming the high specificity of K_Ca3.1 labeling. Due to the methoxy moiety at the B-atom and the additional oxyethylene unit in the spacer, 9 b exhibits higher polarity, which improves solubility and handling without reduction of fluorescence quantum yield. Docking studies using a cryo-electron microscopy (EM) structure of the K_Ca3.1 channel confirmed the interaction of 9 a and 9 b with a binding pocket in the channel pore.     

Characteristics of a NaOH-Activated Blast Furnace Slag Blended with a Fine Particle Silica Waste

Mortars of blast furnace slag blended with a geothermal silica waste at various replacement levels of 0%, 5%, 10%, 15%, and 20% were cured for up to 90 days. The binder was activated by 6 wt% Na₂O equivalent of sodium hydroxide. Lime was added as an activating agent and also to promote pozzolanic reaction with the silica. It was found that the presence of the silica waste increased the reactivity of the cementitious materials, as measured by means of nonevaporable water. The compressive strength was increased in the presence of the silica, except at the highest replacement level of 20%, the optimum silica replacement was that of 5%–10%. The microstructures of blended slag showed less porosity than those of neat slag mortars. The lime was completely consumed after 90 days of hydration.     

Geometric criteria of hydrogen bonds in proteins and identification of `bifurcated' hydrogen bonds

Empirical criteria for identification of hydrogen bonds wereanalyzed to produce a set of geometrically consistent criteria.For a data set of 30 structures, application of a set of purelygeometrical criteria, along with exclusion of abnormal backboneconformations, also excluded a common interaction of Ser/Thrside chains with Asp/Glu side chains ([ST]/[DE] pairs). Theseinteractions were termed `bifurcated hydrogen bonds/', whichimplies delocalization of a positively charged hydrogen of hydroxylbetween the two acceptor atoms of the carboxylic group. These`bifurcated/' interactions are among the most common packingpatterns for [ST]/[DE] pairs of side chains. Therefore, theidentification of hydrogen bonds cannot be based on geometricalcriteria only and requires introduction of some physico-chemicalcriteria.