Exactly alternating silarylene–siloxane polymers. VII. Thermal stability and degradation behavior of p-silphenylene–siloxane polymers with methyl,vinyl, hydrido,and/or fluoroalkyl side groups

The thermal stability and degradation behavior of a series of nine different exactly alternating silphenylene-siloxane polymers which contained methyl, vinyl, hydrido, 3,3,3-trifluoropropyl, and tridecafluoro-1,1,2,2-tetrahydrooctyl side groups, or their combinations, were investigated by dynamic and isothermal gravimetric analyses in air and in nitrogen. Two distinctly different mechanisms were observed in these atmospheres: a complex multi-step weight loss process in air and a single-step process in nitrogen. In nitrogen all polymers produced black, insoluble, highly stable degradation residues which were characterized by high carbon content. In contrast, in air the nonfluorine containing polymers degraded to pure silica, while the fluoroalkyl substituted polymers may have formed fluorosilicates of unspecified structures. There appears to be no significant molecular weight effect on the thermal stability of these polymers, at least not above an M _w value of about 35,000. Isothermal investigations indicate that 300°C in air and 350°C in nitrogen may be possible upper use temperatures for the methylvinyl substituted, exactly alternating silphenylene–siloxane polymers for extended periods of time. A strong thermostabilizing effect by vinyl side groups on the degradation behavior of these polymers was established. The extent of stabilization depends on the content of vinyl units, but it can already be clearly seen at the 5 mol % vinyl level, and it increases exponentially with increasing vinyl concentration. In contrast to this behavior, by comparison with the parent all-methyl substituted, exactly alternating silphenylene–siloxane polymers, the hydrido and fluroalkyl side groups reduce overall polymer thermal stability in terms of the degradation onset temperature, the temperature for 50% weight loss, and the amount of degradation residue. The presence of these groups also extends the later stages of the degradation processes to higher temperatures. Based on these and previous results, an order of stability is proposed as a function of the type of the substituent side groups for the thermal degradation of these polymers.     

Probing Interfacial Electronic and Catalytic Properties on Well‐Defined Surfaces by Using In Situ Raman Spectroscopy

Heterogeneous metal interfaces play a key role in determining the mechanism and performance of catalysts. However, in situ characterization of such interfaces at the molecular level is challenging. Herein, two model interfaces, Pd and Pt overlayers on Au single crystals, were constructed. The electronic structures of these interfaces as well as effects of crystallographic orientation on them were analyzed by shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) using phenyl isocyanide (PIC) as a probe molecule. A clear red shift in the frequency of the C≡N stretch (ν_NC) was observed, which is consistent with X‐ray photoelectron spectroscopy (XPS) data and indicates that the ultrathin Pt and Pd layers donate their free electrons to the Au substrates. Furthermore, in situ electrochemical SHINERS studies showed that the electronic effects weaken Pt?C/Pd?C bonds, leading to improved surface activity towards CO electrooxidation.     

Norm attaining functionals on

It is shown that for any infinite compact Hausdorff space , the Bishop-Phelps set in is of the first Baire category when has the supremum norm.

     

Open science grid study of the coupling between conformation and water content in the interior of a protein

Computational grids are a promising resource for modeling complex biochemical processes such as protein folding, penetration of gases or water into proteins, or protein structural rearrangements coupled to ligand binding. We have enabled the molecular dynamics program CHARMM to run on the Open Science Grid. The implementation is general, flexible, easily modifiable for use with other molecular dynamics programs and other grids and automated in terms of job submission, monitoring, and resubmission. The usefulness of grid computing was demonstrated through the study of hydration of the Glu-66 side chain in the interior of protein staphylococcal nuclease. Multiple simulations started with and without two internal water molecules shown crystallographically to be associated with the side chain of Glu-66 yielded two distinct populations of rotameric states of Glu-66 that differed by as much as 20%. This illustrates how internal water molecules can bias protein conformations. Furthermore, there appeared to be a temporal correlation between dehydration of the side chain and conformational transitions of Glu-66. This example demonstrated how difficult it is to get convergence even in the relatively simple case of a side chain oscillating between two conformations. With grid computing, we also benchmarked the self-guided Langevin dynamics method against the Langevin dynamics method traditionally used for temperature control in molecular dynamics simulations and showed that the two methods yield comparable results.     

Testing of a hot- and cold-wire probe to measure simultaneously the speed and temperature in supercritical CO2 flow

The use of hot-wire anemometry in carbon dioxide flow under supercritical conditions has been analyzed and implemented for the first time. A two-sensor probe to simultaneously measure streamwise velocity and temperature in this flow has been designed and constructed. A calibration and test flow loop that can provide supercritical state conditions above the critical point has been also designed, fabricated and tested. The temperature and velocity flow fields of the flow loop can be varied at constant pressure. It has been found that, above the pseudo-critical temperature, the velocity sensor response fits King’s cooling law with a high correlation coefficient. The dependence of the King’s law parameters on temperature can be accurately presented with second or higher order polynomial or exponential fits, depending on the extent of the temperature range. Below the pseudocritical temperature the data is scattered, and the variation with temperature of the King’s law parameters, determined from calibration, is irregular. The influence on this data scatter of the strong variation of the fluid properties near the critical point is analyzed, and a possibility to reduce it is proposed. The temperature sensor response both above and below the pseudocritical temperature is similar to the response under normal conditions. It is linear with a very high correlation coefficient between the calibration data and the fitted curve. It is also shown that the temperature response is not affected by variation of the flow’s speed.     

Study of Novel Peptides for Antimicrobial Protection in Solution and on Cotton Fabric

Some new N- and C-modified biomolecular peptide analogues of both VV-hemorphin-5 and VV-hemorphin-7 with varied amino acids (Cys, Glu, His), 1-adamantanecarboxylic acid, and niacin (nicotinic acid) were synthesized by solid-phase peptide synthesis—Fmoc (9-fluorenylmethoxy-carbonyl) chemistry and were characterized in water solutions with different pH using spectroscopic and electrochemical techniques. Basic physicochemical properties related to the elucidation of the peptide structure at physiological pH have been also studied. The results showed that the interaction of peptide compounds with light and electricity preserves the structural and conformational integrity of the compounds in the solutions. Moreover, textile cotton fibers were modified with the new compounds and the binding of the peptides to the surface of the material was proved by FTIR and SEM analysis. Washing the material with an alkaline soap solution did not show a violation of the modified structure of the cotton. Antiviral activity against the human respiratory syncytial virus (HRSV-S2) and human adenovirus serotype 5 (HAdV-5), the antimicrobial activity against B. cereus and P. aeruginosa used as model bacterial strains and cytotoxic effect of the peptide derivatives and modified cotton textile material has been evaluated. Antimicrobial tests showed promising activity of the newly synthesized compounds against the used Gram-positive and Gram-negative bacteria. The compounds C-V, H-V, AC-V, and AH-V were found slightly more active than NH7C and NCH7. The activity has been retained after the deposition of the compounds on cotton fibers.     

Dimethyl‐methylphenyl copolysiloxanes by dimethylsilanolate‐initiated ring opening polymerization. Evidence for linearity of the resulting polymer structures

Recently, we reported that dimethylsilanolate‐initiated anionic ring opening polymerization of dimethylsiloxy‐ and diphenylsiloxy‐cyclic siloxanes results in polymer chain branching by dimethylsilanolate‐induced cleavage of only one Si‐C_Ar side bond in diphenylsiloxy repeat units, leading to formation of “Ph‐T‐branches”, and not extending to the cleavage of the second phenyl group. We attributed this behavior to electronic structures of the participating dimethylsiloxy‐, diphenylsiloxy and Ph‐T‐branch silicons and predicted that copolymers prepared by this synthetic route from dimethylsiloxy‐ and methylphenylsiloxy‐cyclics should not undergo branching at all but should have perfect linear chain configuration. Here, we describe results of a study of two such dimethylsilanolate‐initiated ring opening polymerizations of dimethylsiloxy‐ and methyphenylsiloxy‐cyclic tetramers and characterization of the resulting polymers by SEC‐MALS‐VIS, Mark‐Houwink‐Sakurada relationship and ²⁹Si NMR. The results obtained clearly confirmed our prediction of expected linearity of these polymer chains and also indicated that the resulting polymers were completely amorphous even at as low methylphenylsiloxy‐content as 3.9 mol %. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1122–1129     

Synthesis of New Modified with Rhodamine B Peptides for Antiviral Protection of Textile Materials

Here we report on the synthesis and characterization of three new N-modified analogues of hemorphin-4 with rhodamine B. Modified with chloroacetyl, chloride cotton fabric has been dyed and color coordinates of the obtained textile materials were determined. Antiviral and virucidal activities of both the peptide-rhodamine B compounds and the dyed textile material were studied. Basic physicochemical properties (acid-base behavior, solvent influence, kinetics) related to the elucidation of structural activity of the new modified peptides based on their steric open/closed ring effect were studied. The obtained results lead to the conclusion that in protic solvent with change in pH of the environment, direct control over the dyeing of textiles can be achieved. Both the new hybrid peptide compounds and the modification of functionalized textile materials with these bioactive hemorphins showed virucidal activity against the human respiratory syncytial virus (HRSV-S2) and human adenovirus serotype 5 (HAdV-5) for different time intervals (30 and 60 min) and the most active compound was Rh-3.     

Highly Elastic Super-Macroporous Cryogels Fabricated by Thermally Induced Crosslinking of 2-Hydroxyethylcellulose with Citric Acid in Solid State

Biopolymer materials have been considered a “green” alternative to petroleum-based polymeric materials. Biopolymers cannot completely replace synthetic polymers, but their application should be extended as much as possible, exploiting the benefits of their low toxicity and biodegradability. This contribution describes a novel strategy for the synthesis of super-macroporous 2-hydroxyethylcellulose (HEC) cryogels. The method involves cryogenic treatment of an aqueous solution of HEC and citric acid (CA), freeze drying, and thermally induced crosslinking of HEC macrochains by CA in a solid state. The effect of reaction temperature (70–180 °C) and CA concentration (5–20 mass % to HEC) on the reaction efficacy and physico-mechanical properties of materials was investigated. Highly elastic cryogels were fabricated, with crosslinking carried out at ≥100 °C. The storage modulus of the newly obtained HEC cryogels was ca. 20 times higher than the modulus of pure HEC cryogels prepared by photochemical crosslinking. HEC cryogels possess an open porous structure, as confirmed by scanning electron microscopy (SEM), and uptake a relatively large amount of water. The swelling degree varied between 17 and 40, depending on the experimental conditions. The degradability of HEC cryogels was demonstrated by acid hydrolysis experiments.     

Repeated passing principle for propagation in optical resonators

In this paper we make comparison between a well-known theoretical model of light propagation through racetrack resonator and experimentally obtained results. Observed differences are studied and some original modifications are made in the existing model so as to achieve better alignment with experiment. The influence of several geometric parameters on racetrack’s response is used for further adjustments to be performed. This procedure opens up the possibility to estimate the free spectral range and resonant wavelength for different geometric parameters and consequently to predict resonator functionality and working conditions, as well as functionality of complex photonic devices based on resonant structures.