Synthesis and gas permeation parameters of metathesis polytricyclononenes with pendant Me3E‐groups (E = C,Si, Ge)

Metathesis polytricyclononenes were synthesized via ROMP polymerization in the presence of the 1‐st generation Grubbs catalyst and their gas‐transport properties were studied for the first time. The aim of this work was to evaluate the influence of Me₃E‐groups (E = C, Si, Ge) on gas permeation parameters of ROMP materials. New metathesis poly(3‐tert‐butyltricyclononene‐7) and poly(3‐trimethylgermyltricyclononene‐7) were obtained with high yields (up to 95%) and high‐molecular weights (M_w～3–7×10⁵ g mol^?1). The glass transition temperatures of the ROMP polytricyclononenes with Me₃E‐groups decreased when E was changed from C to Si and then to Ge. It was shown that the polytricyclononene containing Me₃Si‐groups has the highest gas permeability while the polytricyclononene containing Me₃C‐substituents has the lowest gas permeability. In addition, the gas permeation parameters were estimated for ROMP Me₃Si‐ and Me₃Ge‐substituted polytricyclonona‐3,7‐dienes. So the influence of the second double bond in the monomer units on the permeability of the polymers obtained was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41395.     

Synthesis of single-walled carbon nanotubes using hemoglobin-based iron catalyst

Hemoglobin (Hb) was used as a catalyst for the growth of single-walled carbon nanotubes (SWCNTs). Hb was deposited onto a hydrophilic treated substrate by spin coating method. After oxidation at 800 °C, protein chains were decomposed and iron oxide nanoparticles remained with an average diameter of 2.29 nm. High quality SWCNTs were synthesized with an average diameter of 1.22 nm. The protein chains prevent iron atoms aggregation and so the size of the nanoparticles is smaller than that from ferritin-like proteins.     

The concept of a near-field Raman probe

This article considers the possibility to use tips, which are functionalised by Raman active molecules, as new Raman probes for near-field optics in such a way that the Raman spectrum can be recorded of such a tip. If the Raman spectrum of the probe molecules is sensitive to their immediate environment, the probe can be used to map a surface by its local influence on the Raman spectrum of the probe. This new concept may be very promising for the investigation of specific interactions at the nanoscale by an optical response. Examples of the sensitivity of such a probe to the local environment are presented as a basis for further development of such a probe.     

Activity–Composition Relations of Chromium Oxide in Silicate Melts at 1500°C under Strongly Reducing Conditions

The solubility and activity–composition relations of chromium oxide in melts of the systems CaO–CrO _x –SiO₂ and CaO–Al₂O₃–CrO _x –SiO₂ have been determined at 1500°C by equilibrating melts with Pt–Cr alloys at known oxygen pressures. It is shown that the increase in the concentration of divalent chromium ions, as the oxygen pressure and the basicity of melt decrease, results in a dramatic increase in the solubility of chromium oxide in the liquid phase. An increase in the Al₂O₃ content of the melt leads to a decrease in the solubility of chromium oxide over the whole composition range studied. The activity coefficient of CrO has been found to increase with increasing melt basicity and decreasing oxygen pressure whereas the activity coefficient of CrO_1.5 decreases sharply with increasing melt basicity for siliceous melts but levels off at a basicity ratio (wt% CaO/wt% SiO₂) of about 0.7. An increase in the Al₂O₃ content of the melts results in an increase in the activity coefficient of CrO.     

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

Titania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO₂ microparticles via a straightforward controlled surface‐initiated polymerization method.     

Stereoselective Formation of 1,4‐Anhydro‐2‐C‐carboxytetritols in the Degradation of 1,5‐Anhydroribitol and 1,5‐Anhydroxylitol with Oxygen in Aqueous Alkali

Abstract

In addition to other acid products, degradation of 1,5‐anhydroribitol (5) and 1,5‐anhydroxylitol (6) with oxygen in 1.25 M NaOH produced diastereomeric 1,4‐anhydro‐2‐C‐carboxy‐D‐erythritol (7) and 1,4‐anhydro‐2‐C‐carboxy‐D‐threitol (8) and their enantiomers as major products. However, the ratio of the diastereomers differed for the two reactants. Thus, their formation could not proceed solely by benzilic acid‐type rearrangements through α‐dicarbonyl intermediates as typically proposed for formation of alkyl C‐carboxyfuranosides from alkyl glycopyranosides in similar reactions. The α‐dicarbonyl species that can form from 5 and 6 are identical. Potential mechanisms to account for stereoselective formation of 7 and 8 are presented.     

Influence of corrosion and mechanical loads on advanced ceramic components

Advanced oxide ceramics are prospective materials for severe application conditions, including corrosion, particularly, in oxygen-rich environments, combined with the action of mechanical loads. The corrosion behavior and mechanical strength decrease of oxide ceramics, such as high alumina, alumina–mullite and zirconia-based ceramics, were studied in water steam supercritical conditions (elevated temperatures and pressures). The strength decrease under the action of the studied aggressive environment is mostly dealt with the glassy phase dissolution and intergranular corrosion for alumina–mullite and high alumina ceramics, while degradation of zirconia-based ceramics is also dealt with the phase transformation. The influence of structure defects related to processing of the ceramics on corrosion is considered.     

Numerical Simulation of Anisotropic Shrinkage in a 2D Compact of Elongated Particles

Microstructural evolution during simple solid-state sintering of two-dimensional compacts of elongated particles packed in different arrangements was simulated using a kinetic, Monte Carlo model. The model used simulates curvature-driven grain growth, pore migration by surface diffusion, vacancy formation, diffusion along grain boundaries, and annihilation. Only the shape of the particles was anisotropic; all other extensive thermodynamic and kinetic properties such as surface energies and diffusivities were isotropic. We verified our model by simulating sintering in the analytically tractable cases of simple-packed and close-packed, elongated particles and comparing the shrinkage rate anisotropies with those predicted analytically. Once our model was verified, we used it to simulate sintering in a powder compact of aligned, elongated particles of arbitrary size and shape to gain an understanding of differential shrinkage. Anisotropic shrinkage occurred in all compacts with aligned, elongated particles. However, the direction of higher shrinkage was in some cases along the direction of elongation and in other cases in the perpendicular direction, depending on the details of the powder compact. In compacts of simple-packed, mono-sized, elongated particles, shrinkage was higher in the direction of elongation. In compacts of close-packed, mono-sized, elongated particles and of elongated particles with a size and shape distribution, the shrinkage was lower in the direction of elongation. The results of these simulations are analyzed, and the implication of these results is discussed.     

AICAR Protects Vascular Endothelial Cells from Oxidative Injury Induced by the Long-Term Palmitate Excess

Hyperlipidemia manifested by high blood levels of free fatty acids (FFA) and lipoprotein triglycerides is critical for the progression of type 2 diabetes (T2D) and its cardiovascular complications via vascular endothelial dysfunction. However, attempts to assess high FFA effects in endothelial culture often result in early cell apoptosis that poorly recapitulates a much slower pace of vascular deterioration in vivo and does not provide for the longer-term studies of endothelial lipotoxicity in vitro. Here, we report that palmitate (PA), a typical FFA, does not impair, by itself, endothelial barrier and insulin signaling in human umbilical vein endothelial cells (HUVEC), but increases NO release, reactive oxygen species (ROS) generation, and protein labeling by malondialdehyde (MDA) hallmarking oxidative stress and increased lipid peroxidation. This PA-induced stress eventually resulted in the loss of cell viability coincident with loss of insulin signaling. Supplementation with 5-aminoimidazole-4-carboxamide-riboside (AICAR) increased endothelial AMP-activated protein kinase (AMPK) activity, supported insulin signaling, and prevented the PA-induced increases in NO, ROS, and MDA, thus allowing to maintain HUVEC viability and barrier, and providing the means to study the long-term effects of high FFA levels in endothelial cultures. An upgraded cell-based model reproduces FFA-induced insulin resistance by demonstrating decreased NO production by vascular endothelium.     

Interferon-β Activity Is Affected by S100B Protein

Interferon-β (IFN-β) is a pleiotropic cytokine secreted in response to various pathological conditions and is clinically used for therapy of multiple sclerosis. Its application for treatment of cancer, infections and pulmonary diseases is limited by incomplete understanding of regulatory mechanisms of its functioning. Recently, we reported that IFN-β activity is affected by interactions with S100A1, S100A4, S100A6, and S100P proteins, which are members of the S100 protein family of multifunctional Ca²⁺-binding proteins possessing cytokine-like activities (Int J Mol Sci. 2020;21(24):9473). Here we show that IFN-β interacts with one more representative of the S100 protein family, the S100B protein, involved in numerous oncological and neurological diseases. The use of chemical crosslinking, intrinsic fluorescence, and surface plasmon resonance spectroscopy revealed IFN-β binding to Ca²⁺-loaded dimeric and monomeric forms of the S100B protein. Calcium depletion blocks the S100B–IFN-β interaction. S100B monomerization increases its affinity to IFN-β by 2.7 orders of magnitude (equilibrium dissociation constant of the complex reaches 47 pM). Crystal violet assay demonstrated that combined application of IFN-β and S100B (5–25 nM) eliminates their inhibitory effects on MCF-7 cell viability. Bioinformatics analysis showed that the direct modulation of IFN-β activity by the S100B protein described here could be relevant to progression of multiple oncological and neurological diseases.