Polymer-Derived SiOC/ZrO2 Ceramic Nanocomposites with Excellent High-Temperature Stability

Polymer-derived SiOC/ZrO₂ ceramic nanocomposites have been prepared using two synthetic approaches. A commercially available polymethylsilsesquioxane (MK Belsil PMS) was filled with nanocrystalline zirconia particles in the first approach. The second method involved the addition of zirconium tetra( n -propoxide), Zr(OⁿPr)₄, as zirconia precursor to polysilsesquioxane. The prepared materials have been subsequently cross-linked and pyrolyzed at 1100°C in argon atmosphere to provide SiOC/ZrO₂ ceramics. The obtained SiOC/ZrO₂ materials were characterized by means of X-ray diffraction, elemental analysis, Raman spectroscopy as well as transmission electron microscopy. Furthermore, annealing experiments at temperatures from 1300° to 1600°C have been performed. The annealing experiments revealed that the incorporation of ZrO₂ into the SiOC matrix remarkably increases the thermal stability of the composites with respect to crystallization and decomposition at temperatures exceeding 1300°C. The results obtained within this study emphasize the enormous potential of polymer-derived SiOC/ZrO₂ composites for high-temperature applications.     

Cigarette Smoke Affects ABCAl Expression via Liver X Receptor Nuclear Translocation in Human Keratinocytes

Cutaneous tissue is the first barrier against outdoor insults. The outer most layer of the skin, the stratum corneum (SC), is formed by corneocytes embedded in a lipid matrix (cholesterol, ceramide and fatty acids). Therefore, the regulation of lipids and, in particular, of cholesterol homeostasis in the skin is of great importance. ABCA1 is a membrane transporter responsible for cholesterol efflux and plays a key role in maintaining cellular cholesterol levels. Among the many factors that have been associated with skin diseases, the environmental stressor cigarette smoke has been recently studied. In the present study, we demonstrate that ABCA1 expression in human cells (HaCaT) was increased (both mRNA and protein levels) after CS exposure. This effect was mediated by the inhibition of NFkB (aldehydes adducts formation) that allows the translocation of liver X receptor (LXR). These findings suggest that passive smoking may play a role in skin cholesterol levels and thus affect cutaneous tissues functions.     

Synthesis and Biological Testing of N‐Aminoimidazole‐Based p38α MAP Kinase Inhibitors

The p38 mitogen‐activated protein (MAP) kinase α plays a central role in the regulation of cellular responses such as differentiation, proliferation, apoptosis, and inflammation. Inhibition of p38 results in decreased synthesis of pro‐inflammatory cytokines. To date, diverse p38α inhibitors are in phase II clinical trials for numerous cytokine‐dependent diseases. 2‐Sulfanylimidazole derivatives offer advantages over the prototype inhibitor SB 203580, including fewer cytochrome P450 interactions and better kinetic properties. The aim of this study was to develop novel 1,2,4,5‐tetrasubstituted pyridinylimidazoles with acyl residues at the imidazole N1 position that can interact with the kinase's hydrophobic region II (HR II) or sugar pocket (SP) to improve both selectivity and activity. The substitution pattern was optimized by variation of the acyl moiety at the N1 position of the N‐aminoimidazole core. Acylation of the amino function was used for optimization and led to potent p38α MAPK inhibitors.     

Modeling and biological investigations of an unusual behavior of novel synthesized acridine-based polyamine ligands in the binding of double helix and G-quadruplex DNA

Three novel 2,7-substituted acridine derivatives were designed and synthesized to investigate the effect of this functionalization on their interaction with double-stranded and G-quadruplex DNA. Detailed investigations of their ability to bind both forms of DNA were carried out by using spectrophotometric, electrophoretic, and computational approaches. The ligands in this study are characterized by an open-chain (L1) or a macrocyclic (L2, L3) framework. The aliphatic amine groups in the macrocycles are joined by ethylene (L2) or propylene chains (L3). L1 behaved similarly to the lead compound m-AMSA, efficiently intercalating into dsDNA, but stabilizing G-quadruplex structures poorly, probably due to the modest stabilization effect exerted by its protonated polyamine chains. L2 and L3, containing small polyamine macrocyclic frameworks, are known to adopt a rather bent and rigid conformation; thus they are generally expected to be sterically impeded from recognizing dsDNA according to an intercalative binding mode. This was confirmed to be true for L3. Nevertheless, we show that L2 can give rise to efficient π-π and H-bonding interactions with dsDNA. Additionally, stacking interactions allowed L2 to stabilize the G-quadruplex structure: using the human telomeric sequence, we observed the preferential induction of tetrameric G-quadruplex forms. Thus, the presence of short ethylene spacers seems to be essential for obtaining a correct match between the binding sites of L2 and the nucleobases on both DNA forms investigated. Furthermore, current modeling methodologies, including docking and MD simulations and free energy calculations, provide structural evidence of an interaction mode for L2 that is different from that of L3; this could explain the unusual stabilizing ability of the ligands (L2>L3>L1) toward G-quadruplex that was observed in this study.     

Glutathione-S-transferase polymorphism, metallothionein expression, and mercury levels among students in Austria

BACKGROUND: Detoxification is an essential process in all living organisms. Humans accumulate heavy metals primarily as a result of lifestyle and environmental contamination. However, not all humans experience the estimated individual exposure. This suggests the presence of genetic regulatory mechanisms. OBJECTIVE: In order to identify genetic factors underlying the inter-individual variance in detoxification capacity for the heavy metal mercury, 192 students were investigated. We focused on the relationship between polymorphisms in glutathione-S-transferase (GST) genes and mercury concentrations in blood, urine, and hair. The correlation between blood mercury levels, GSTT1 and GSTM1 polymorphism, and gene expression of certain metallothionein subgroups (MT1, MT3) was evaluated in a further group of students (N=30). METHODS: Mercury levels in acid digested samples were measured by cold vapor AAS. Genotyping of the GSTT1 and GSTM1-gene deletion polymorphism was performed by means of PCR. Gene expression of several MT genes was analyzed in lymphocytes from fresh peripheral blood by semiquantitative RT-PCR. RESULTS: The following was noted: a) hair mercury concentrations are significantly increased in persons with the double deleted genotype (GSTT1-/- and GSTM1-/-) as compared to persons with the intact genotype, and b) MT1X expression is higher in persons with the intact genotype (GSTT1+/+ and GSTM1+/+). CONCLUSIONS: We conclude that the epistatic effect of the GSTT1 and the GSTM1 deletion polymorphism is a risk factor for increased susceptibility to mercury exposure. The relationship between MT gene expression and GST gene polymorphisms needs further investigation. If MT expression depends on GST polymorphisms it would have important implications on the overall metal detoxification capability of the human organism.     

Baseline water quality and macrophyte assemblages in Pampean streams: a regional approach

Streams of the pampas region (central Argentina) are characterized by the lack of riparian forests and by low current velocities, and receive a large amount of industrial and domestic effluents. Intensive agriculture in the region has greatly increased during the last years; nevertheless, regional studies to determine baseline conditions are not available. Here, we characterized pampean streams considering physico-chemical water features and the composition of macrophyte communities, and we established if the regions proposed by an early hydrological regionalization show differentiated water chemistry and macrophyte assemblages. Forty-one streams were sampled in autumn, spring and summer. Streams were characterized by alkaline waters, with high conductivities and dissolved oxygen concentrations, and they can be classified as eutrophic. A good discrimination among regions was achieved based on streamwater features in all seasons; variables that most contribute to the discrimination were related to pH, eutrophication, and conservative ions. Regional differences may be due to variations in water availability, parent material, and land use practices. The aquatic plant communities reflected the eutrophic state of waters, but macrophyte composition was not useful to differentiate among regions because it is not affected by differences in water chemistry. Macrophyte species grouped according to their growth form and assemblage distribution were related to chemical variables (as conductivity and nitrate) and possibly to flow conditions.     

Adsorption behaviors and mechanisms of porous hypercrosslinked polymers with adjustable functional groups toward doxycycline hydrochloride from water

Imino hypercrosslinked polymers (NH-HCPs), amino hypercrosslinked polymers (NH₂-HCPs), and carboxyl hypercrosslinked polymers (COOH-HCPs) were synthesized through cross-linking and Friedel-Crafts reactions to serve as highly efficient adsorbents for doxycycline hydrochloride (DOX) in water. These polymers, NH-HCPs, NH₂-HCPs, and COOH-HCPs, exhibited specific surface areas measuring 450, 267.576, and 94.39 m²/g, respectively. The adsorption kinetics of DOX onto these polymers were consistent with the pseudo-second-order model, while the adsorption isotherms followed the Langmuir model (NH-HCPs) and Freundlich model (NH₂-HCPs and COOH-HCPs), respectively. The maximum DOX adsorption capacities for NH-HCPs, NH₂-HCPs, and COOH-HCPs were 166.82, 132.43, and 72.07 mg/g, respectively. Simulation results indicated that COOH-HCPs exhibited the strongest adsorption capability due to a substantial presence of oxygen and nitrogen groups on its surface, enabling the formation of hydrogen bonds with DOX. However, its actual adsorption capacity was the lowest among the polymers, indicating that structural adjustments played a more significant role in improving adsorption performance compared to functional adjustments. Adsorption experiments conducted with NH-HCPs and NH₂-HCPs further supported this hypothesis. The primary DOX adsorption mechanism of NH-HCPs, NH₂-HCPs, and COOH-HCPs involved the H-bonding of oxygen and nitrogen functional groups, along with other mechanisms such as π-π conjugated effects, pore-filling effects, electrostatic interactions, and acid–base interactions. Overall, this study demonstrates the effectiveness of NH-HCPs, NH₂-HCPs, and COOH-HCPs in DOX removal from water, highlighting the significant influence of structural adjustments on adsorption performance.     

Composites produced from waste plastic with agricultural and energy sector by-products

A three-stage route to chemically upcycle post-consumer poly(ethylene terephthalate) (PET) to produce high compressive strength composites is reported. This procedure involves initial glycolysis with diethylene glycol to produce a mixture (GPET) comprising oligomers of 2–7 terephthalate units followed by trans/esterification of GPET with fatty acid chains supplied by brown grease, an agricultural by-product of animal fat of relatively low nutritional or fuel value. This process yields PGB comprising a mixture of mono-terephthalate ester derivatives. The olefin units provided by unsaturated fatty acid chains in brown grease were crosslinked by an inverse vulcanization reaction with elemental sulfur to give composites GBS_x (x = wt% S, varied from 80%–90%). The compressive strengths of GBS₈₀ (27.5 ± 2.6 MPa) and GBS₉₀ (19.2 ± 0.8 MPa) exceed the compressive strength required of ordinary Portland cement (17 MPa) for its use in residential building foundations. The current route represents a way to repurpose waste plastic, energy sector by-product sulfur, and agricultural by-product brown grease to give high strength composites with mechanical properties suggesting their possible use to replace less sustainably sourced legacy structural materials.