Soybean‐Oil‐Based Thermosetting Resins with Methacrylated Vanillyl Alcohol as Bio‐Based,Low‐Viscosity Comonomer

A novel, bio‐based, aromatic monomer (methacrylated vanillyl alcohol, MVA) is synthesized using vanillyl alcohol and methacrylic anhydride in the absence of solvents. The resulting MVA is used as a sustainable comonomer to replace styrene in a maleinated acrylated epoxidized soybean‐oil (MAESO) resin to produce novel thermosets via free radical polymerization. The influence of MVA loading on the viscosity, gelation time, curing extent, thermomechanical properties, and tensile properties of the MAESO–MVA thermoset is investigated. The synthesized MVA exhibits very low volatility, which is beneficial for the development of construction material with low or zero emission. The viscosity of the MAESO–MVA system can be tailored to meet the commercial requirements. Increasing the MVA content accelerates the crosslinking reaction rate and improves thermal and mechanical properties of the MAESO–MVA system. The glass transition temperature increases with increasing MVA content. Soxhlet extraction experiments show that more than 90% of the components are incorporated into the crosslinking network. Overall, the developed MVA monomer shows promising properties to be used as an effective, green comonomer to replace styrene.     

Photopinking of white PVC products: A kind of magic

Short‐term photoeffects like photograying, photobluing, and photopinking are well‐known in the polyvinyl chloride (PVC) industry. While photobluing and photograying are well understood regarding their mechanisms of occurrences there are still some missing facts. Furthermore, there are three different types of pinking effects with three different mechanisms and consequently three different ways to avoid this discoloration of mainly white PVC products. The recent paper is focusing on one hand of the photopinking of PVC products, which are stabilized with nitrogen‐containing, organic stabilizer whose mechanism was not explained until today. In the past there was neither a method to analyze nor to simulate this type of photopinking. However, the discovery of a charge transfer complex between the nitrogen‐containing substance and nitric acid gave the basic idea to investigate this phenomenon by photo‐electromotive force investigations of titanium dioxide and the nitrogen‐containing substance and by cyclo voltammetry. On the other hand, the authors are attempting to supplement the findings regarding the mechanism of the photopinking of white window profiles which are lead stabilized and which were installed north‐facing in cooler areas with high humidity. Again, a simulation and the analysis of the color‐giving substance of the north‐faced photopinking were impossible in the past. The authors assumed that antioxidants might play an important rule for this type of discoloration. They supported their hypothesis by synthesis of quinoid structures based on antioxidants, spectroscopic investigations, artificial weathering, and electrochemical calculations. J. VINYL ADDIT. TECHNOL., 24:195–207, 2018. © 2016 Society of Plastics Engineers     

Bismuth niobate thin films for dielectric energy storage applications

Low‐temperature processed bismuth niobate (BNO) thin films were explored in this work as a potential candidate for high‐energy density capacitors. The BNO samples were fabricated by the chemical solution deposition method followed by a series of ultraviolet (UV) exposure and heat treatments. A UV treatment prior to the final pyrolysis step was found to be useful in eliminating bound carbon. X‐ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) demonstrated that the residual carbon could be effectively removed at 350°C after UV exposure. Following a heat treatment at 450°C, the energy storage density of the BNO thin film reached 39 J/cm³ with an efficiency of 72%. Furthermore, 350°C and 375°C treated BNO samples showed high‐temperature stability such that the efficiencies of the films remained above 97% up to 150°C at 10 kHz under 1 MV/cm applied field.     

Thin water films and particle morphology evolution in nanocrystalline MgO

A key question in the field of ceramics and catalysis is how and to what extent residual water in the reactive environment of a metal oxide particle powder affects particle coarsening and morphology. With X‐ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), we investigated annealing‐induced morphology changes on powders of MgO nanocubes in different gaseous H₂O environments. The use of such a model system for particle powders enabled us to describe how adsorbed water that originates from short exposure to air determines the evolution of MgO grain size, morphology, and microstructure. While cubic nanoparticles with a predominant abundance of (100) surface planes retain their shape after annealing to T = 1173 K under continuous pumping with a base pressure of water p(H₂O) = 10^?5 mbar, higher water partial pressures promote mass transport on the surfaces and across interfaces of such particle systems. This leads to substantial growth and intergrowth of particles and simultaneously favors the formation of step edges and shallow protrusions on terraces. The mass transfer is promoted by thin films of water providing a two‐dimensional solvent for Mg²⁺ ion hydration. In addition, we obtained direct evidence for hydroxylation‐induced stabilization of (110) faces and step edges of the grain surfaces.     

Chiral control of enantiomers through crystallization: Moving from ternary phase diagrams to design spaces

Although chiral purity is a critical quality attribute for many synthetic drugs, current industrial strategies for establishing chiral purity control are underdeveloped. Such strategies have relied on the construction of ternary phase diagrams, system classification, and case‐specific operating policies. These policies have been developed to provide enantiopure solids, regardless of product specification or target. In this article, new operating policies are developed for obtaining solids that meet, but do not exceed, chiral purity specifications for arbitrary systems. These policies can provide significant yield improvements over the current practice. Additionally, this work provides an approach for the creation of design spaces based on the collection of limited, small scale data. This approach has been extended to sequential re‐crystallizations and can be used to determine “global” optimal policies within a synthetic route. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3323–3331, 2018     

Porous concrete as a template for the synthesis of porous carbon materials

The potential of industrial porous concrete for using as a template for the synthesis of porous carbon materials has been investigated. Carbon replicas of porous concrete have been prepared by carbonization of sucrose. The pores of the resulting carbon materials range from the macropore to the micropore region, pointing to a hierarchy.     

Liquid phase growth of graphene on silicon carbide

We developed a novel method to produce graphene on silicon carbide (SiC) at a temperature as low as 1000 °C. The method is based on liquid phase growth (LPG) of graphene mediated by liquid gallium, which acts not only as a flux to store carbon dissolved from a surface of SiC when heated, but also as a catalyst to promote the formation of graphene on SiC when cooled. Our experimental results revealed that gallium-treated SiC substrates are coated with uniform and continuous graphene films. The LPG method is able to supply graphene films consisting of one to several hundreds of layers, depending on heating temperatures. Our approach can not only provide an alternative way to form graphene natively on SiC, but will also bring a technological breakthrough in industrial applications of graphene, e.g. the realization of graphene-on-insulator substrates.     

Stable Synthetic Bacteriochlorins for Photodynamic Therapy: Role of Dicyano Peripheral Groups,Central Metal Substitution (2H,Zn, Pd), and Cremophor EL Delivery

A series of four stable synthetic bacteriochlorins was tested in vitro in HeLa cells for their potential in photodynamic therapy (PDT). The parent bacteriochlorin (BC), dicyano derivative (NC)₂BC and corresponding zinc chelate (NC)₂BC–Zn and palladium chelate (NC)₂BC–Pd were studied. Direct dilution of a solution of bacteriochlorin in an organic solvent (N,N‐dimethylacetamide) into serum‐containing medium was compared with the dilution of bacteriochlorin in Cremophor EL (CrEL; polyoxyethylene glycerol triricinoleate) micelles into the same medium. CrEL generally reduced aggregation (as indicated by absorption and fluorescence) and increased activity up to tenfold (depending on bacteriochlorin), although it decreased cellular uptake. The order of PDT activity against HeLa human cancer cells after 24 h incubation and illumination with 10 J cm^?2 of near‐infrared (NIR) light is (NC)₂BC–Pd (LD₅₀=25 nM ) > (NC)₂BC > (NC)₂BC–Zn ≈ BC. Subcellular localization was determined to be in the endoplasmic reticulum, mitochondria and lysosomes, depending on the bacteriochlorin. (NC)₂BC–Pd showed PDT‐mediated damage to mitochondria and lysosomes, and the greatest production of hydroxyl radicals as determined using a hydroxyphenylfluorescein probe. The incorporation of cyano substituents provides an excellent motif for the enhancement of the photoactivity and photostability of bacteriochlorins as PDT photosensitizers.