The use of microwave irradiation for the easy synthesis of graphene-supported transition metal nanoparticles in ionic liquids

Stable ruthenium or rhodium metal nanoparticles were supported on chemically derived graphene (CDG) surfaces with small and uniform particle sizes (Ru 2.2 ± 0.4 nm and Rh 2.8 ± 0.5 nm) by decomposition of their metal carbonyl precursors by rapid microwave irradiation in a suspension of CDG in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. The graphene-supported hybrid nanoparticles were shown to be active and could be re-used at least 10 times as catalysts for the hydrogenation of cyclohexene and benzene under organic-solvent-free conditions with constant activities up to 1570 mol cyclohexane × (mol metal)⁻¹ × h⁻¹ at 4 bar and 75 °C.     

Modeling and in-depth analysis of the start-up of dividing-wall columns

Saving potentials of up to 30% in capital and operating costs are the driving forces behind the increase in the application of dividing-wall columns in industry. However, a lack of knowledge still exists when dealing with the start-up of dividing-wall columns, which is inherently a strongly nonlinear process. Here, for the first time the start-up of dividing-wall columns is explored, where the starting point is an empty column at ambient conditions. A model is presented which is capable of predicting the dynamic discrete-continuous changes which are characteristic of dividing-wall columns. The proposed process model takes into account the heat transfer across the dividing wall as well as the vapor distribution below the dividing wall. The degree of accuracy of the model is clearly determined by comparing different simplifications, e.g. a constant vapor distribution ratio equal to the steady-state value. The detailed studies were carried out with strict product specifications so that the influence of process parameters could be quantified. The rigorous process model and the obtained simulation results presented in this study provide a promising basis for developing and applying optimal start-up policies for dividing-wall columns.     

New light-sensitive nucleosides for caged DNA strand breaks

Phototriggered bod cleavage has found wide application in chemistry as well as in biology. Nevertheless, there are only a few methods available for site-specific photochemical induction of DNA strand scission despite numerous potential applications. In this study we report the development of new photocleavable nucleotides based on the photochemistry of o-nitrobenzyl esters. The light-sensitive moieties were generated through introduction of o-nitrophenyl groups at the 5'C position of the nucleoside sugar backbone. The newly synthesized, modified nucleosides were incorporated in oligonucleotides and are able to build stable DNA duplexes. In such a way modified oligonucleotides ca cleaved site-specifically upon irradiation with > 360 nm light with high efficiency. Furthermore, we show that these modifications can be bypassed in DNA synthesis promoted by Thermus aquaticus DNA polymerase.     

铝酸钙系冶金熔剂和CaF2对镁碳砖的侵蚀比较

为了降低精炼渣对钢包渣线镁碳砖的侵蚀,分别以20%(w)的冶金熔剂铝酸钙、铝镁酸钙和CaF2与80%(w)的初始钢渣配制成三种精炼渣,以镁碳砖为感应炉的坩埚,在坩埚内放入钢样,待钢样熔化并升温到1 600℃时,加精炼渣持续冶炼5 h(期间共更换渣8次),冷却后测镁碳砖渣线部位的侵蚀(渗透)深度并进行SEM分析。结果表明:以铝酸钙和铝镁酸钙为熔剂的精炼渣都比以CaF2为熔剂的精炼渣对镁碳砖的渗透浅、侵蚀小,而以铝镁酸钙冶金熔剂为精炼渣比以铝酸钙冶金熔剂为精炼渣对镁碳砖的渗透和侵蚀性都大大降低。这是由于铝镁酸钙中含有饱和的MgO,减缓了镁碳砖中MgO向CMA渣中的溶解,从而降低了渣对镁碳砖的侵蚀。     

Real-Time Monitoring of (E)-β-Farnesene Emission in Colonies of the Pea Aphid, Acyrthosiphon pisum, Under Lacewing and Ladybird Predation

Aphids (Homoptera) are constantly under attack by a variety of predators and parasitoids. Upon attack, most aphids release alarm pheromone that induces escape behavior in other colony members, such as dropping off the host plant. In the pea aphid, Acyrthosiphon pisum Harris (Aphididae), the only component of this alarm pheromone is the sesquiterpene (E)-β-farnesene (EBF). EBF is thought to act as a kairomone by attracting various species of parasitoids and predators including lacewings and ladybirds. Lately, it also was proposed that EBF is constantly emitted in low quantities and used by aphids as a social cue. No study has focused on emission dynamics of this compound over a long time period. Here, we present the first long-time monitoring of EBF emission in aphid colonies using real-time monitoring. We used a zNose^TM to analyze the headspace of colonies of the pea aphid, under lacewing (Neuroptera: Chrysopidae) and ladybird (Coleoptera: Coccinellidae) predation, over 24 hr. We found no emission of EBF in the absence of predation. When either a ladybird adult or a lacewing larva was placed in an aphid colony, EBF was detected in the headspace of the colonies in the form of emission blocks; i.e., periods in which EBF was emitted alternating with periods without EBF emission. The number of emission blocks correlated well with the number of predation events that were determined at the end of each experiment. There was no circadian rhythm in alarm pheromone emission, and both predators were active during both night and day. Our results show that alarm pheromone emission pattern within an aphid colony is driven by the feeding behavior of a predator.     

Problems with and local solutions for organic matter management in Vietnam

Soil organic matter plays a major role in sustainable agricultural development in Vietnam. A general soil evaluation shows that the content of organic matter in most soil units in Vietnam ranges between 0.5 to 3.0% soil organic matter (in the A and B horizon only) with lower levels especially on sloping land. Most upland soils (70% that contain ≤ 2% soil organic matter) are in danger due to imminent soil erosion. Soil organic matter is lost very quickly due to erosion, lack of organic manure and poor farming techniques in these areas. Using green hedgerows along contour lines and intercropping with legume species to cover the soil are technological options to control soil erosion and improve soil organic matter content on sloping land. Green hedgerows significantly reduce soil and organic matter loss by 50–70%, compared to sloping land without hedgerows. Intercropping with legume species reduces soil loss by 40–50%, and can provide the soil with 2.5–12 tons of green manure/ha/year. However, more studies are needed to identify the best technologies for managing soil organic matter in upland areas. This revised version was published online in June 2006 with corrections to the Cover Date.     

Improved thin film stability of differently formulated,printed, and crosslinked polymer layers against successive solvent printing

Interface control remains a top challenge of solution-processed organic light emitting diodes (OLED) stacks since the device performance heavily relies on it. Film stability of an inkjet deposited and crosslinked layer against subsequent exposure to a suitable inkjet printed solvent has been investigated. Impact of processing solvent (solvent used to prepare the polymer layer) on solution-cast thin film properties has already been shown for polymer films. To our knowledge, this study is the first one analyzing thin films stability against solvent exposure using technology relevant materials processed via inkjet printing (IJP). The outcome of this research showed that the stability of the crosslinked films is affected by the solvent used for ink formulation. These findings are of great interest for multilayered semiconductors devices, such as OLEDs, field-effect transistors and dye-sensitized solar cells. Differential scanning calorimetry (DSC) was used to quantify the efficiency of the polymer crosslinking reaction in pure powder and in thin films, as processed from different solvents. Crosslinking efficiency measured by DSC correlated well with the deformation induced by the solvent and observed on layer surfaces. The interaction in solution between polymer and solvent has also been evaluated to explain its impact on thin film stability against successive solvent printing. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48895.     

Bifunctional DNA Duplexes Permit Efficient Incorporation of pH Probes into Liposomes

Enzyme-mediated proton transport across biological membranes is critical for many vital cellular processes. pH-sensitive fluorescent dyes are an indispensable tool for investigating the molecular mechanism of proton-translocating enzymes. Here, we present a novel strategy to entrap pH-sensitive probes in the lumen of liposomes that has several advantages over the use of soluble or lipid-coupled probes. In our approach, the pH sensor is linked to a DNA oligomer with a sequence complementary to a second oligomer modified with a lipophilic moiety that anchors the DNA conjugate to the inner and outer leaflets of the lipid bilayer. The use of DNA as a scaffold allows subsequent selective enzymatic removal of the probe in the outer bilayer leaflet. The method shows a high yield of insertion and is compatible with reconstitution of membrane proteins by different methods. The usefulness of the conjugate for time-resolved proton pumping measurements was demonstrated by using two large membrane protein complexes.     

From Oxadiazole to Triazole Analogues: Optimization toward a Dual Orexin Receptor Antagonist with Improved in vivo Efficacy in Dogs

The orexin system is responsible for regulating the sleep-wake cycle. Suvorexant, a dual orexin receptor antagonist (DORA) is approved by the FDA for the treatment of insomnia disorders. Herein, we report the optimization efforts toward a DORA, where our starting point was (5-methoxy-4-methyl-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-[5-(2-trifluoromethoxy-phenyl)-[1,2,4]oxadiazol-3-yl]-pyrrolidin-1-yl}methanone ( 6 ), a compound which emerged from our in-house research program. Compound 6 was shown to be a potent, brain-penetrating DORA with in vivo efficacy similar to suvorexant in rats. However, shortcomings from low metabolic stability, high plasma protein binding (PPB), low brain free fraction (f_u brain), and low aqueous solubility, were identified and hence, compound 6 was not an ideal candidate for further development. Our optimization efforts addressing the above-mentioned shortcomings resulted in the identification of (4-chloro-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-methyl-2-[5-(2-trifluoromethoxy-phenyl)-4H-[1,2,4]triazol-3-yl]-pyrrolidin-1-yl}l-methanone ( 42 ), a DORA with improved in vivo efficacy compared to 6 .