Systematic Control of the Orientation of Organic Phosphorescent Pt Complexes in Thin Films for Increased Optical Outcoupling

Orienting light‐emitting molecules relative to the substrate is an effective method to enhance the optical outcoupling of organic light‐emitting devices. Platinum(II) phosphorescent complexes enable facile control of the molecular alignment due to their planar structures. Here, the orientation of Pt(II) complexes during the growth of emissive layers is controlled by two different methods: modifying the molecular structure and using structural templating. Molecules whose structures are modified by adjusting the diketonate ligand of the Pt complex, dibenzo‐(f,h)quinoxaline Pt dipivaloylmethane, (dbx)Pt(dpm), show an ≈20% increased fraction of horizontally aligned transition dipole moments compared to (dbx)Pt(dpm) doped into a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl, CBP, host. Alternatively, a template composed of highly ordered 3,4,9,10‐perylenetetracarboxylic dianhydride monolayers is predeposited to drive the alignment of a subsequently deposited emissive layer comprising (2,3,7,8,12,13,17,18‐octaethyl)‐21H,23H‐porphyrinplatinum(II) doped into triindolotriazine. This results in a 60% increase in horizontally aligned transition dipole moments compared to the film deposited in the absence of the template. The findings provide a systematic route for controlling molecular alignment during layer growth, and ultimately to increase the optical outcoupling in organic light‐emitting diodes.     

A High-Voltage,Dendrite-Free,and Durable Zn–Graphite Battery

The intrinsic advantages of metallic Zn, like high theoretical capacity (820 mAh g⁻¹), high abundance, low toxicity, and high safety have driven the recent booming development of rechargeable Zn batteries. However, the lack of high-voltage electrolyte and cathode materials restricts the cell voltage mostly to below 2 V. Moreover, dendrite formation and the poor rechargeability of the Zn anode hinder the long-term operation of Zn batteries. Here a high-voltage and durable Zn–graphite battery, which is enabled by a LiPF₆-containing hybrid electrolyte, is reported. The presence of LiPF₆ efficiently suppresses the anodic oxidation of Zn electrolyte and leads to a super-wide electrochemical stability window of 4 V (vs Zn/Zn²⁺). Both dendrite-free Zn plating/stripping and reversible dual-anion intercalation into the graphite cathode are realized in the hybrid electrolyte. The resultant Zn–graphite battery performs stably at a high voltage of 2.8 V with a record midpoint discharge voltage of 2.2 V. After 2000 cycles at a high charge–discharge rate, high capacity retention of 97.5% is achieved with ≈100% Coulombic efficiency.     

Soybean unsaponifiables: Hydrocarbons from deodorizer condensates

Molecular distillation of deodorizer condensates followed by chromatography on alumina, gave substantial quantities of hydrocarbons free of other unsaponifiable constituents. Squalene comprised 50% of the hydrocarbon fraction and contained practically all the unsaturation. A crystalline, saturated hydrocarbon fraction of 4.2% was composed primarily of C₂₉ and C₃₁ paraffins. An unresolved fraction was composed of two major components, each estimated to contain about 30 or 35 carbon atoms. Minor amounts of many hydrocarbons with chain lengths of 15\s-35 carbon atoms were present but not completely identified. C¹⁴ analysis showed that the hydrocarbons are natural to soybean oil and they are not artifacts arising from petroleum solvent residues. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, USDA.     

Fumonisin B1 alters cell cycle progression and interleukin-2 synthesis in swine peripheral blood mononuclear cells

Fumonisin B1 (FB1) is a mycotoxin produced by Fusarium verticillioides, a fungus that commonly contaminates maize. In the present study, we investigated the effects of FB1 on swine peripheral blood mononuclear cells (PBMC) by measuring cell proliferation, cell cycle progression and interleukin (IL)-2 production. Forty-eight hours after treatment in vitro, FB1 induced a decrease of PBMC proliferation as measured by cell counting and dehydrogenase enzyme activity. This effect was observed starting with 10 microM FB1. The effect of FB1 on cell cycle progression was analyzed by flow cytometry. Incubation of PBMC with FB1 increased the percentage of cells blocked in G0/G1 phase of the cell cycle. Treatment with 200 microM FB1 induces a high blockade of the cell cycle, with 92.4% of cells in G0/G1 phase. This blockade was observed in all lymphocyte subsets tested (CD2+, CD4+, CD8+ and Ig+) as evidenced by dual staining for DNA and membrane surface molecules. A significant decrease of IL2 production was also observed in the supernatants of ConA stimulated PBMC treated with 100 or 200 microM FB1. In conclusion, these data suggest that FB1 may affect immune functions by inhibiting lymphocyte proliferation and IL2 production, suggesting a possible role of FB1 exposure during infectious disease and cancer.     

Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging

Gas-water mass transfer and the transport of dissolved gases in variably saturated porous media are key processes for in-situ remediation by pulsed gas sparging. In this context, gas dissolution tests were conducted during pulsed oxygen gas injection into sand columns. The columns were recharged with anoxic water, effluents were analyzed for dissolved O2, and tracer tests were performed to detect accumulation of trapped gas. In a second series oxygen gas was blended with sulfur hexafluoride (SF6), and O2 and SF6 breakthrough curves were recorded. To interpret experimental results, a numerical model was applied that simulates multi-species kinetic mass transfer during gas dissolution. The model predicted breakthrough curves of dissolved gas species and delivered spatially resolved values for gas phase accumulation and composition, which are not directly accessible experimentally. It was shown how dissolved nitrogen accumulates increasingly in trapped gas phase and inhibits its complete dissolution, in case the pulsed gas injections were operated based on O2 breakthrough only. Accumulation of nitrogen also retarded dissolved oxygen transport and thus oxygen breakthrough. Experiments plus modeling demonstrated that SF6 measurements are highly sensitive to the gas dissolution processes, and provide a more sensitive criterion for determining gas injection frequencies during pulsed biosparging.     

Influence of boron and oxygen on the microstructure and mechanical properties of high-strength Ti66Nb13Cu8Ni6.8Al6.2 alloys

The influence of boron additions and different oxygen contamination levels on the microstructure and the mechanical properties in the Ti_66?xNb₁₃Cu₈Ni_6.8Al_6.2B_x (0 ? x ? 1) system were investigated. The alloys were prepared by levitation copper mould casting as rods with a diameter of 5 mm using different grades of starting elements. The alloy without boron exhibits a maximum compressive stress of more than 2500 MPa, associated with a compressive strain of more than 30%. The ultimate tensile stress is ～1075 MPa with a maximum elongation of 1.6%. Increased oxygen content leads to a rise of yield strength due to solid solution hardening. Boron additions promote grain refinement and reinforce the interdendritic phase compound by forming needle-like TiB precipitates. This change in microstructure increases the yield stress and the Young’s modulus and lowers the plastic strain. The microstructure was analysed in terms of the boron content by means of scanning electron microscopy, Auger electron spectroscopy and transmission electron microscopy. The presented mechanical properties are compared with the compression and tensile properties of the commercially available Ti6Al4V ELI (ELI = extra low interstitial) alloy.     

Tailor‐Made Polymer Multilayers

The fabrication of multilayer assemblies from polymeric compounds is an important tool for precise control of film architecture on the nanoscale. In this report, a general, novel approach for the preparation of well‐defined polymeric multilayers is described. To achieve this, sulfonyl‐azide group containing polymers are first generated and deposited as thin films onto solid (organic) substrates. Upon thermal activation, the system crosslinks and binds to the substrate via C–H bond insertion. Through step‐and‐repeat procedures, multilayer assemblies are then generated where all the individual layers are linked to each other. As the assembly process does not require any specific molecular interactions, the described process represents a general strategy to generate tailor‐made multilayer surface coatings with wide range of film thickness and composition.     

Masked mycotoxins: A review

The aim of this review is to give a comprehensive overview of the current knowledge on plant metabolites of mycotoxins, also called masked mycotoxins. Mycotoxins are secondary fungal metabolites, toxic to human and animals. Toxigenic fungi often grow on edible plants, thus contaminating food and feed. Plants, as living organisms, can alter the chemical structure of mycotoxins as part of their defence against xenobiotics. The extractable conjugated or non‐extractable bound mycotoxins formed remain present in the plant tissue but are currently neither routinely screened for in food nor regulated by legislation, thus they may be considered masked. Fusarium mycotoxins (deoxynivalenol, zearalenone, fumonisins, nivalenol, fusarenon‐X, T‐2 toxin, HT‐2 toxin, fusaric acid) are prone to metabolisation or binding by plants, but transformation of other mycotoxins by plants (ochratoxin A, patulin, destruxins) has also been described. Toxicological data are scarce, but several studies highlight the potential threat to consumer safety from these substances. In particular, the possible hydrolysis of masked mycotoxins back to their toxic parents during mammalian digestion raises concerns. Dedicated chapters of this article address plant metabolism as well as the occurrence of masked mycotoxins in food, analytical aspects for their determination, toxicology and their impact on stakeholders.