Carbocations as Lewis Acid Catalysts: Reactivity and Scope

One class of potential Lewis acids that has received negligible attention as a catalyst is the carbocation. Here we show the potential of triarylmethylium ions as highly powerful Lewis acid catalysts for organic reactions. The Lewis acidity of the triarylmethylium ion can be easily tuned by variation of the electronic properties of the aromatic rings and the catalytic activity of the carbocation is shown to correlate directly to the level of stabilization of the empty p_C‐orbital at the cationic carbon. The versatility of triarylmethylium ions as efficient Lewis acid catalysts for organic reactions is demonstrated in Diels–Alder, aza‐Diels–Alder, conjugate addition, halogenation, epoxide rearrangement and intramolecular hetro‐ene reactions.

     

Oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides

The oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides is reported. High yields of olefins and only moderate formation of carbon oxides was observed. Both are primary products that hardly interconvert under the reaction conditions used. Addition of chloride increases the rate of reaction, while slightly decreasing the selectivity to olefins. The addition of carbon dioxide strongly decreases the rate of reaction, the negative order of 0.5 indicating that two active Li⁺sites are blocked by the adsorption of one CO₂molecule. The reaction proceeds at low oxygen pressure primarily via elimination of dihydrogen, while at higher oxygen partial pressure the hydrogen elimination occurs via water formation. It is speculated that dehydrogenation and cracking involve Li⁺and a rather nucleophilic oxygen site.     

Lipase-based quantitation of triacylglycerols in cellular lipid extracts: Requirement for presence of detergent and prior separation by thin-layer chromatography

A protocol, based on the use of Pseudomonas lipase, is presented to measure quantitatively the amount of triacylglycerols in extracts from cultured cells or tissues. Since the lipase also acts on di- and monoacylglycerols, separation of the extracts by thin-layer chromatography is recommended. In order to allow the lipase-catalyzed hydrolysis to proceed efficiently, lipid extracts or eluates from silica scraping were mixed with the detergent Thesit [dodecylpoly(ethylene glycol ether)], prior to drying. After dissolution of the dried residues in water, the amount of triacylglycerols was quantified using Pseudomonas sp. lipase, glycerol kinase, glycerol-phosphate oxidase, and peroxidase. The activity of the latter enzyme was followed either colorimetrically in the presence of 4-aminoantipyrine and 2,4,6-tribromo-3-hydroxybenzoic acid or fluorimetrically in the presence of homovanillic acid.     

Biopolymer foams from Novatein thermoplastic protein and poly(lactic acid)

A batch processing method is used to fabricate foams comprising of a blend of poly(lactic acid) (PLA) and Novatein, a protein‐based thermoplastic. Various compositions of Novatein/PLA are prepared with and without a compatibilizer, PLA grafted with itaconic anhydride (PLA‐g‐IA). Pure Novatein cannot form a cellular structure at a foaming temperature of 80 °C, however, in a blend with 50 wt % of PLA, microcells form with smaller cell sizes (3.36 µm) and higher cell density (8.44 × 10²¹ cells cm^?3) compared to pure PLA and blends with higher amounts of PLA. The incorporation of 50 wt % of semicrystalline Novatein stiffens the amorphous PLA phase, which restrains cell coalescence and cell collapse in the blends. At a foaming temperature of 140 °C, NTP₃₀–PLA₇₀ shows a unique interconnected porous morphology which can be attributed to the CO₂‐induced plasticization effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45561.     

Pulsatile Jet Cleaning of Filter Cloths Contaminated with Yeast Cells

The cleaning of filter cloths is necessary to avoid prolonged system downtime and strong fouling. Reliable cleaning concepts are central to the removal of residues from the complex surface of filter cloths. Particle residues, in particular, play a decisive role in the sufficiency of the cleaning performance. Consequently, enhanced particle‐removal cleaning concepts based on pulsatile jets for filter cloths have been developed. By varying the cleaning parameters, it has been demonstrated that increased pulse numbers and velocities improve the cleaning performance. Furthermore, this promising cleaning concept cleaned more effectively than conventional methods. The reduction in the amount of detergent needed is an ecological and economic advantage of pulsatile cleaning.     

Cleanability of Surfaces from Active Pharmaceutical Ingredient Surrogate Riboflavin by Falling Film

Falling films in wash down process are of major interest for pharmaceutical isolators, which are used for processing of highly potent pharmaceutical products. In this study multiple process parameters were examined with common materials of isolator systems. The importance of material and surface finish in respect of cleanability and complete wetting as well as a combination of process parameters are presented and discussed. For cleaning validation an effect of high interest was discovered: swab sampling areas changed their properties over many repeated cycles and showed decreased cleanability.     

Heterodera schachtii Nematodes Interfere with Aphid-Plant Relations on Brassica oleracea

Aboveground and belowground herbivore species modify plant defense responses differently. Simultaneous attack can lead to non-additive effects on primary and secondary metabolite composition in roots and shoots. We previously found that aphid (Brevicoryne brassicae) population growth on Brassica oleracea was reduced on plants that were infested with nematodes (Heterodera schachtii) prior (4 weeks) to aphid infestation. Here, we examined how infection with root-feeding nematodes affected primary and secondary metabolites in the host plant and whether this could explain the increase in aphid doubling time from 3.8 to 6.7 days. We hypothesized that the effects of herbivores on plant metabolites would depend on the presence of the other herbivore and that nematode-induced changes in primary metabolites would correlate with reduced aphid performance. Total glucosinolate concentration in the leaves was not affected by nematode presence, but the composition of glucosinolates shifted, as gluconapin concentrations were reduced, while gluconapoleiferin concentrations increased in plants exposed to nematodes. Aphid presence increased 4-methoxyglucobrassicin concentrations in leaves, which correlated positively with the number of aphids per plant. Nematodes decreased amino acid and sugar concentrations in the phloem. Aphid population doubling time correlated negatively with amino acids and glucosinolate levels in leaves, whereas these correlations were non-significant when nematodes were present. In conclusion, the effects of an herbivore on plant metabolites were independent of the presence of another herbivore. Nematode presence reduced aphid population growth and disturbed feeding relations between plants and aphids.     

Rheological evaluation of the influence of polymer concentration and molar mass distribution on the formation and performance of asymmetric gas separation membranes prepared by dry phase inversion

Asymmetric gas separation membranes were prepared by the dry-casting technique from PEEKWC, a modified amorphous glassy poly(ether ether ketone). The phase inversion process and membrane performance were correlated to the properties of the polymer and the casting solution (molar mass, polymer concentration, solution rheology and thermodynamics). It was found that a broad molar mass distribution of the polymer in the casting solution is most favourable for the formation of a highly selective membrane with a dense skin and a porous sub-layer. Thus, membranes with an effective skin thickness of less than 1 μm were obtained, exhibiting a maximum O₂/N₂ selectivity of 7.2 and a CO₂/CH₄ selectivity of 39, both significantly higher than in a corresponding thick dense PEEKWC membrane and also comparable to or higher than that of the most commonly used polymers for gas separation membranes. The CO₂ and O₂ permeance were up to 9.5×10⁻³ and 1.8×10⁻³ m³/(m² h bar) (3.5 and 0.67 GPU), respectively.