Properties of the acrylic acid polymers obtained by atmospheric pressure plasma polymerization

Plasma polymers of acrylic acid were obtained using an atmospheric pressure discharge system. The plasma polymerization reactor uses a dielectric barrier discharge, with the polyethylene terephthalate dielectric acting as substrate for deposition. The plasma was characterized by specific electrical measurements, monitoring the applied voltage and the discharge current. Based on the spatially resolved optical emission spectroscopy, we analyzed the distribution of the excited species in the discharge gap, specific plasma temperatures (vibrational and gas temperatures) being calculated with the Boltzmann plot method. The properties of the plasma polymer films were investigated by contact angle measurements, infrared and UV-Vis spectroscopy, scanning electron microscopy. The films produced by plasma polymerization at atmospheric pressure showed a hydrophilic character, in correlation with the strong absorbance of OH groups in the FTIR spectrum. Moreover, the surface of the plasma polymers at micrometric scale is smooth and free of defects without particular features.     

Olaparib-Based Photoaffinity Probes for PARP-1 Detection in Living Cells

The poly-ADP-ribose polymerase (PARP) is a protein from the family of ADP-ribosyltransferases that catalyzes polyadenosine diphosphate ribose (ADPR) formation in order to attract the DNA repair machinery to sites of DNA damage. The inhibition of PARP activity by olaparib can cause cell death, which is of clinical relevance in some tumor types. This demonstrates that quantification of PARP activity in the context of living cells is of great importance. In this work, we present the design, synthesis and biological evaluation of photo-activatable affinity probes inspired by the olaparib molecule that are equipped with a diazirine for covalent attachment upon activation by UV light and a ligation handle for the addition of a reporter group of choice. SDS-PAGE, western blotting and label-free LC-MS/MS quantification analysis show that the probes target the PARP-1 protein and are selectively outcompeted by olaparib; this suggests that they bind in the same enzymatic pocket. Proteomics data are available via ProteomeXchange with identifier PXD018661.     

Studies on the shear stability of macromolecular additives by size exclusion chromatography

Factors affecting the mechanical stability of polyalkylmethacrylate type additives are comparatively examined for different shear degradation test methods and routine engine service, taking into account rheological and size exclusion chromatography data. The shear test methods are assessed regarding the MWD of the degraded additives. The extent of degradation of macromolecular additives and the molecular weight distribution (MWD) of the degraded products depend on the nature and extent of shear stress, average molecular weight, MWD, chemical structure, nature of the base oil and temperature. The shape of the MWD of the sonicated and automotive service subject additives was found to be similar, unlike that of the additives sheared by the diesel injector method. These are narrower and more dependent on the initial MWD of the additive, especially in the case of the additives with broader MWD. A shear test that better correlates with service has to take into account not only the control of shear stress, by appropriate calibration, but also a suitable degradation mechanism.     

The influence of lubricating fluid type on the properties of biodegradable greases

The lubricating ability of a grease depends on both the base oil and the thickener. As a result of their intrinsic properties and/or because of their com‐patibility with thickeners and specific additives, base fluids have different influences upon the properties of grease formulations. It is well known that mineral oils are the most widely used lubricant bases due to their inherent lubricity and lower cost, but recent environmental concern has led to consideration of the use of vegetable oils and readily biodegradable synthetic fluids as raw materials in lubricating grease formulations. As well as the base materials, the additives for biodegradable greases should also be biodegradable. This requirement limits the kind of products that may be used in environmentally friendly greases. This paper presents comparative data concerning the tribological and physico‐chemical properties of biodegradable greases formulated with certain vegetable oils, such as rape seed oil, castor oil, and soybean oil or their mixtures, and synthetic esters. The improvement of the load‐carrying properties of biodegradable greases and the antioxidative effect of some suitable additives have also been studied, and the results are presented here.     

A new freeze-drying device for platinum replica studies of cell surface and cytoskeleton: An example using immunogold-labeled human erythrocytes

We designed and built a freeze-drying device that ensures the protection of the specimens against contaminants during mounting on the cold stage of the freeze-fracture machine, transferring into the vacuum chamber and deep etching. The device consists of a copper cap that covers the specimen and a thermal connection that ensures thermal transfer between the microtome arm and the copper cap. This device was used to study the ultrastructural features of the erythrocyte membrane skeleton and the immunocytchemical localization of spectrin in an “in situ” approach, by freeze drying and platinum rotary shadowing. Human erythrocytes adhered to polylysine-coated coverslips and were broken by a stream of buffer that mimics the intracellular ionic environment (“inside buffer”). The samples were prefixed in periodate-lysine-paraformaaldehyde fixative, labeled with antispectrin 5-nm gold particles, fixed in glutaraldehyde, mordanted in tannic acid, postfixed in OsO₄, repeatedly washed in water, rinsed quickly in 30% ethanol, freeze-dried, and rotary-shadowed. Electron microscopic examination of the replicas revealed the skeletal network on the inner surface of the erythrocyte membrane. Immunocytochemical labeling proved that spectrin represents a fibrillar component of the network. Our data confirm the speculative model of the molecular organization of the erythrocyte skeleton, based on studies on in vitro association of proteic constituents. Both the technique and the device developed by us may lead to a deeper understanding of the spatial organization of the cytoskeletal network of more complex cell types.     

Simultaneous single-loop multimaterial and multijoint topology optimization

As the aerospace and automotive industries continue to strive for efficient lightweight structures, topology optimization (TO) has become an important tool in this design process. However, one ever-present criticism of TO, and especially of multimaterial (MM) optimization, is that neither method can produce structures that are practical to manufacture. Optimal joint design is one of the main requirements for manufacturability. This article proposes a new density-based methodology for performing simultaneous MMTO and multijoint TO. This algorithm can simultaneously determine the optimum selection and placement of structural materials, as well as the optimum selection and placement of joints at material interfaces. In order to achieve this, a new solid isotropic material with penalization-based interpolation scheme is proposed. A process for identifying dissimilar material interfaces based on spatial gradients is also discussed. The capabilities of the algorithm are demonstrated using four case studies. Through these case studies, the coupling between the optimal structural material design and the optimal joint design is investigated. Total joint cost is considered as both an objective and a constraint in the optimization problem statement. Using the biobjective problem statement, the tradeoff between total joint cost and structural compliance is explored. Finally, a method for enforcing tooling accessibility constraints in joint design is presented.     

High surface area Mo–V–Te–Nb–O catalysts: Preparation, characterization and catalytic behaviour in ammoxidation of propane

Mo–V–Te–Nb mixed oxides with a molar ratio of 1:0.30:0.20:0.15 were prepared by citrate and dry-up method, both associated with hydrothermal treatments in the presence of a cationic surfactant (cetyl trimethylammonium bromide, CTAB), and tested in the ammoxidation of propane. The catalysts were characterized by adsorption–desorption isotherms of nitrogen at 77 K, particle size measurements, XRD, and XPS. By using the surfactant, the surface area increased significantly, and samples with surface area between 110 and 239 m²/g were obtained. These catalysts exhibited a propane conversion near 48% with selectivity to acrylonitrile of about 32% for a space velocity 30 times higher than generally reported.     

Moving Droplets in 3D Using Light

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical “fuel,” a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s^?1 toward or away from the irradiation source as a result of a light‐induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a “cargo” and moving the new larger droplet to a “reactor” droplet where the cargo undergoes a chemical reaction. The control and versatility of this light‐activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.     

Supported Co-based perovskites as catalysts for total oxidation of methane

Supported LaCoO₃ perovskites with 2, 5, 10, 15, 20 and 30 wt.% loading were prepared by impregnation of a Ce_0.8Zr_0.2O₂ support (40 m² g⁻¹) with: (i) a solution of La and Co nitrates and (ii) a “citrate” solution, namely containing La and Co nitrates, and citric acid. All precursors were decomposed and calcined at 700 °C for 5 h. XRD investigations indicated the formation of a pure perovskite phase only if citrates were used. These materials were tested as catalysts for methane combustion in the temperature range 300–700 °C. All catalysts showed a lower T₅₀ (the temperature at which the conversion level of methane is 50%) than the Ce_0.8Zr_0.2O₂ support or non-supported LaCoO₃. The activity increased continuously with the perovskite loading. The samples prepared from citrates were slightly more active than from nitrates. This is due to a more homogeneous surface, as indicated by XPS measurements. The presence of a well-characterized perovskite phase (as opposed to highly dispersed elements) seems necessary for good activity. A higher reaction rate per perovskite weight is observed for low loadings when compared to bulk LaCoO₃, but the variation with perovskite loading presents a breakpoint, suggesting complex interactions in the catalysts or in the oxidation mechanism.

In spite of the experimental impossibility to evaluate the area developed by the supported perovskite, an approximative approach strongly suggests a synergy between the support and supported species.     

Optical waveguide amplifier in Nd-doped glass written with near-IRfemtosecond laser pulses

A near-IR (775 nm) femtosecond laser has been used to directly write a 1 cm long optical waveguide in Nd-doped silicate glass. A gain of 1.5 dB/cm was obtained at a signal wavelength of 1054 nm for ~346 mW of 514 nm pump power, in front of the input coupling objective