Influence of Electron Beam Irradiation on High‐Temperature Mechanical Properties of Ethylene Vinyl Acetate/Carbon Fibers Composites

The purpose of this study was to investigate the effect of carbon fiber (CF) and electron‐beam (EB) radiation on high‐temperature mechanical properties of ethylene‐vinyl acetate (EVA). Polymer composites were prepared by mixing on a two‐roll mill. After compression molding, the samples were irradiated between 60 and 180 kGy, and dynamic mechanical analysis (DMA) was used to characterize physical properties. The effects of filler content and radiation level on the mechanical properties of EVA/CF were evaluated. The shear stress and modulus were observed to increase with increasing of the filler level. However, there was a dramatic decrease in creep compliance. It was also shown that introduction of irradiation on EVA composite increases the shear stress and the real part of the dynamic shear modulus G' due to the increase in molecular weight and cross‐linking of the polymer after irradiation. J. VINYL ADDIT. TECHNOL., 26:325–335, 2020. © 2019 Society of Plastics Engineers     

Novel Flexible Electrochemical Microreactor and its Validation by Three Model Electrosyntheses

A novel flexible electrochemical microreactor has been developed. Flexibility is reached by a modular design, suitability for a broad process parameter range including high pressure operation, and accessibility of production scale. Selected reactor aspects have been validated by applying the reactor to three different electrosyntheses: synthesis of tailor-made mixtures of paraffins by Kolbe electrolysis, cation flow method, and synthesis of peroxodicarbonate. High conversion rates, yields, selectivities, and Faraday efficiency levels have been observed, showing precise process control.     

Physicochemical Methods for Prediction of Functional Information for Proteins

Structural genomics initiatives are determining thousands of new protein structures. Many of these structures are of unknown function, and computational methods for the rapid determination of functional information from protein structure are needed. We present details of how functional information is obtained from the structure using THEMATICS (Theoretical Microscopic Titration Curves). THEMATICS is a computational procedure that gives information about chemical reactivity, based on solution of the Poisson-Boltzmann equations for the electrical potential function. We show how anomalies in predicted titration curves are established. We show further that when residues with anomalous predicted titration curves form a cluster in physical space, these residues tend to be very highly conserved across species and such clusters are reliable predictors of the active site. Results are given for ten enzymes; detailed results are shown for the enzymes triosephosphate isomerase (from chicken), 6-hydroxymethyl-7,8-dihydropterin pyrophosphokinase (from E. coli), and papain (from papaya).     

XPS study of irreversibly adsorbed arsenic on a Pt(1 1 1) electrode

The chemical composition of an irreversibly adsorbed layer of arsenic on Pt(1 1 1) in sulfuric acid solution has been studied by X-ray photoelectron spectroscopy (XPS). From the chemical shift of the As 3d level, a change in the valence state from As(0) to As(III) with positive-going electrode potential is deduced, the total amount of As on the surface remaining constant. The As coverage derived from XPS is around 0.33 ML, which is in agreement with the charge under the current peak in the cyclic voltammogram. From the coadsorption of anions, accompanying the valence transition of As, As(III) is assumed to exist as As(OH)₃ on the surface.     

Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 2: Application to Combustion-Generated Soot Aerosols as a Function of Fuel Equivalence Ratio

Composition, shape factor, size, and fractal dimension of soot aerosol particles generated in a propane/O₂, flame were determined as a function of the fuel equivalence ratio (φ). Soot particles were first size-selected by a differential mobility analyzer (DMA) and then analyzed by an Aerodyne aerosol mass spectrometer (AMS). The DMA provides particles of known mobility diameter (d_m ). The AMS quantitatively measures the mass spectrum of the nonrefractory components of the particles and also provides the vacuum aerodynamic diam eter (d_va ) corresponding to the particles of known mobility diameter. The measured d_m, d_va , and nonrefractory composition are used in a system of equations based on the formulation presented in the companion article to estimate the particle dynamic shape factor, total mass, and black carbon (BC) content. Fractal dimension was estimated based on the mass-mobility relationship. Two types of soot particles were observed depending on the fuel equivalence ratio. Type 1: for φ < 4 (lower propane/O₂), d_va ; was nearly constant and independent of d_m . The value of d_va increased with increasing φ. Analysis of the governing equations showed that these particles were highly irregular (likely fractal aggregates), with a dynamic shape factor that increased with d_m and φ. The fractal dimension of these particles was approximately 1.7. These particles were composed mostly of BC, with the organic carbon content increasing as φ increased. At φ = 1.85, the particles were about 90% BC, 5% PAH, and 5% aliphatic hydrocarbon (particle density = 1.80 g/cm³). Type 2: for φ > 4 (high propane/O₂), d_va was linearly proportional to d_m . Analysis of the governing equations showed that these particles were nearly spherical (likely compact aggregates), with a dynamic shape factor of 1.1 (versus 1 for a sphere) and a fr actal dimension of 2.95 (3 for a sphere). These particles were composed of about 50% PAH, 45% BC, and 5% aliphatic hydrocarbons (particle density = 1.50 g/cm³). These results help interpret some measurement s obtained in recent field studies.     

Numerical Characterization of Particle Beam Collimation: Part II Integrated Aerodynamic-Lens–Nozzle System

As a sequel to our previous effort on the modeling of particle motion through a single lens or nozzle, flows of gas–particle suspensions through an integrated aerodynamic-lens–nozzle inlet have been investigated numerically. It is found that the inlet transmission efficiency (η_t) is unity for particles of intermediate diameters (D_p ～ 30–500 nm). The transmission efficiency gradually diminishes to ～40% for large particles (D_p > 2500 nm) because of impact losses on the surface of the first lens. There is a catastrophic reduction of η_t to almost zero for very small particles (D_p ≤ 15 nm) because these particles faithfully follow the final gas expansion. We found that, for very small particles, particle transmission is mainly controlled by nozzle geometry and operating conditions. A lower upstream pressure or a small inlet can be used to improve transmission of very small particles, but at the expense of sampling rate, or vice versa. Brownian motion exacerbates the catastrophic reduction in η_t for small particles; we found that the overall particle transmission efficiency can be roughly calculated as the product of the aerodynamic and the purely Brownian efficiencies. For particles of intermediate diameters, Brownian motion is irrelevant, and the modeling results show that the transmission efficiency is mainly controlled by the lenses. Results for an isolated lens or nozzle are used to provide guidance for the design of alternative inlets. Several examples are given, in which it is shown that one can configure the inlet to preferentially sample large particles (with η_t > 50% for D_p = 50–2000 nm) or ultrafine particles (with η_t > 50% for D_p = 20–1000 nm). Some of the results have been compared with experimental data, and reasonable agreement has been demonstrated.     

Complexes of Silver(I) Ions and Silver Phosphate Nanoparticles with Hyaluronic Acid and/or Chitosan as Promising Antimicrobial Agents for Vascular Grafts

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes.     

The Role of AKT/mTOR Pathway in Stress Response to UV-Irradiation: Implication in Skin Carcinogenesis by Regulation of Apoptosis,Autophagy and Senescence

Induction of DNA damage by UVB and UVA radiation may generate mutations and genomic instability leading to carcinogenesis. Therefore, skin cells being repeatedly exposed to ultraviolet (UV) light have acquired multilayered protective mechanisms to avoid malignant transformation. Besides extensive DNA repair mechanisms, the damaged skin cells can be eliminated by induction of apoptosis, which is mediated through the action of tumor suppressor p53. In order to prevent the excessive loss of skin cells and to maintain the skin barrier function, apoptotic pathways are counteracted by anti-apoptotic signaling including the AKT/mTOR pathway. However, AKT/mTOR not only prevents cell death, but is also active in cell cycle transition and hyper-proliferation, thereby also counteracting p53. In turn, AKT/mTOR is tuned down by the negative regulators being controlled by the p53. This inhibition of AKT/mTOR, in combination with transactivation of damage-regulated autophagy modulators, guides the p53-mediated elimination of damaged cellular components by autophagic clearance. Alternatively, p53 irreversibly blocks cell cycle progression to prevent AKT/mTOR-driven proliferation, thereby inducing premature senescence. Conclusively, AKT/mTOR via an extensive cross talk with p53 influences the UV response in the skin with no black and white scenario deciding over death or survival.     

Characterization of Cu/CeO2/γ-Al2O3 Thin Film Catalysts by Thermal Desorption Spectroscopy

Thermal desorption spectroscopy (TDS) under ultra high vacuum (UHV) condition has been used to investigate the desorption characteristics of Cu/CeO₂/γ-Al₂O₃ thin film catalysts coated onto the microchannel of a microreactor. TDS results demonstrate that surface desorption profiles and chemical properties (acid–base and redox properties) are remarkably influenced by the catalyst composition, i.e. the loading of copper and ceria. The enhanced basicity with the increase of ceria loading and the decrease of copper loading is evident from the shifted desorption maximum of CO₂ in TDS spectra. Three oxygen species, ranging from weakly bound oxygen desorbed at low temperature to the strongly held lattice oxygen desorbed at high temperature, are easily discernible and clearly identified by O₂ TDS spectra, depending on the catalyst compositions. The concomitant thermal desorption of O₂, CO₂, and H₂O at low temperature indicates the unique chemical properties of copper/ceria catalyst with appropriate copper and ceria contents. The observed low-temperature feature is ascribed to the role of porthole of copper/ceria interfacial area for several desorbed species. The weakly bound oxygen species is attributed to the enhanced abundance of copper/ceria interfacial anionic vacancies created by the intimate contact between copper and ceria entities and its impact on steam reforming of methanol (SRM) reaction is tentatively discussed in terms of reverse oxygen spillover.     

Pd deposition onto Au(111) from nitrate solution

The initial stages of palladium deposition onto Au(111) from 0.1 M HNO₃ + 0.2 mM Pd(NO₃)₂ have been studied by cyclic voltammetry and in situ scanning tunnelling microscopy. It is demonstrated that nucleation starts exclusively at surface defects such as monoatomic high steps, which is at variance with recently published work. From this and our previous work it thus appears that surface defects are the preferred nucleation sites indeed for nitrate, sulphate and chloride containing solutions.