Random and block copolymers based on 4-methyl-1-pentene and 1-pentene

The zirconium acetamidinate catalyst {Cp*Zr(Me)₂[N(Et)C(Me)N(tBu)]} (Cp* = ?⁵-C₅Me₅) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched α-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions.     

Salivary defense proteins: their network and role in innate and acquired oral immunity

There are numerous defense proteins present in the saliva. Although some of these molecules are present in rather low concentrations, their effects are additive and/or synergistic, resulting in an efficient molecular defense network of the oral cavity. Moreover, local concentrations of these proteins near the mucosal surfaces (mucosal transudate), periodontal sulcus (gingival crevicular fluid) and oral wounds and ulcers (transudate) may be much greater, and in many cases reinforced by immune and/or inflammatory reactions of the oral mucosa. Some defense proteins, like salivary immunoglobulins and salivary chaperokine HSP70/HSPAs (70 kDa heat shock proteins), are involved in both innate and acquired immunity. Cationic peptides and other defense proteins like lysozyme, bactericidal/permeability increasing protein (BPI), BPI-like proteins, PLUNC (palate lung and nasal epithelial clone) proteins, salivary amylase, cystatins, prolin-rich proteins, mucins, peroxidases, statherin and others are primarily responsible for innate immunity. In this paper, this complex system and function of the salivary defense proteins will be reviewed.     

Produktionsintegrierter Umweltschutz — Verminderung von Reststoffen,gezeigt anhand ausgeführter Beispiele

Practical examples of production-related environmental protection and volume reduction in residual substances . Minimizing the volume of residual substances produced in chemical production processes is a matter of growing significance. One example is the production of toluylene diisocyanate where HCl gases generated as by-products are reclaimed by a special HCl electrolysis process and subsequently used in the production of precursors for toluylene diisocyanate. Another example is a combined disposal system for sewage sludge and for a particular chlorine-laden residue (a chlorinated hydrocarbon). Once this plant had gone on stream it was possible both to reduce considerably the volume of waste to be dumped in the landfill and to discontinue the incineration of the chlorinated hydrocarbon at sea.     

Analysis of the Influence of Processing Conditions on the Supramolecular Structure and Antioxidant Distribution in PP‐Pipes Using Infrared Microscopy

The supramolecular structure in pipe walls of isotactic PP‐R is a function of compound composition and processing parameters, which both influence the mechanical properties of the pipes. µFTIR shows a gradient of the crystallinity across the pipe wall, with a lower‐crystalline outer layer, and a higher‐crystalline core layer. The rate of extrusion has an influence on the thickness of the outer layer. The nucleating effect on the morphological profile throughout the pipe wall can be visualised. µFTIR shows a homogeneous distribution of the primary antioxidant in the pipe wall. Both the spectral crystallinity and the antioxidant concentration distribution are calculated.

     

Rigid cinchona conformers in enantioselective catalytic reactions: new cinchona‐modified platinum catalysts in the Orito reaction

The use of cinchona alkaloids (cinchonidine, cinchonine, quinine, quinidine, α-isocinchonine, α-isoquinidine, γ-isoquinidine) in the Orito reaction (hydrogenation of ethyl pyruvate and ethyl benzoylformate) strongly supports the structure of the intermediate complex (cinchona alkaloid “anti‐open” conformer–pyruvate 1 : 1 complex); in addition, so far unknown stereochemical conditions have been identified and the utilization of rigid cinchona conformers in the study of asymmetric syntheses have been generalized. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magic Peptide: Unique Properties of the LRR11 Peptide in the Activation of Leukotriene Synthesis in Human Neutrophils

Neutrophil-mediated innate host defense mechanisms include pathogen elimination through bacterial phagocytosis, which activates the 5-lipoxygenase (5-LOX) product synthesis. Here, we studied the effect of synthetic oligodeoxyribonucleotides (ODNs), which mimic the receptor-recognized sites of bacterial (CpG-ODNs) and genomic (G-rich ODNs) DNAs released from the inflammatory area, on the neutrophil functions after cell stimulation with Salmonella typhimurium. A possible mechanism for ODN recognition by Toll-like receptor 9 (TLR9) and RAGE receptor has been proposed. We found for the first time that the combination of the magic peptide LRR11 from the leucine-rich repeat (LRR) of TLR9 with the CpG-ODNs modulates the uptake and signaling from ODNs, in particular, dramatically stimulates 5-LOX pathway. Using thickness shear mode acoustic method, we confirmed the specific binding of CpG-ODNs, but not G-rich ODN, to LRR11. The RAGE receptor has been shown to play an important role in promoting ODN uptake. Thus, FPS-ZM1, a high-affinity RAGE inhibitor, suppresses the synthesis of 5-LOX products and reduces the uptake of ODNs by neutrophils; the inhibitor effect being abolished by the addition of LRR11. The results obtained revealed that the studied peptide-ODN complexes possess high biological activity and can be promising for the development of effective vaccine adjuvants and antimicrobial therapeutics.     

First genetically verified occurrence of Ligula pavlovskii outside its native range and characteristics of its infection in Neogobius fluviatilis

In this study, we provide the first genetically verified distribution record beyond its native range of Ligula pavlovskii, a high-impact endoparasite of Ponto-Caspian gobies. According to parasitological surveys, ligulosis was detected for the first time in monkey goby individuals collected from Lake Balaton in 2004, 34 years after the first record of monkey goby in the lake. During a Lake Balaton survey in 2018, we detected tapeworms in 44.4% of the sampled monkey gobies. This prevalence is about two to ten times higher than it was reported from within the native range of the fish hosts. The same survey revealed an uneven spatial distribution of the ligulosis in the monkey gobies inhabiting different shoreline sections of the lake. We assume that the occurrence and recent distribution data of this high-impact endoparasite may provide useful information for potential biocontrol measures of invasive Ponto-Caspian gobies in the future.     

Delineation of Subsea Freshwater Extension by Marine Geoelectromagnetic Soundings (SE Mediterranean Sea)

This study presents a novel application of marine geoelectromagnetic technique, in an attempt to delineate freshwater extension of the coastal sub-aquifers beneath the SE Mediterranean Sea, along central Israel. The novel marine Ex-Bz time domain electromagnetic (TDEM) geophysical method was applied, demonstrating high sensitivity to the presence of sub-seafloor electrically resistive structures up to several kilometers offshore (shallow marine environment). The study included 19 marine measurements located offshore between Ashdod in the south to Tel-Aviv in the north, where a previous onshore study detected fresh groundwater below seawater intrusion at the coast line. The offshore measurements were conducted to distances of up to 3 km from the shoreline. It was found that the lower sub-aquifer contains fresh groundwater (resistivity >10 Ω-m) to a distance of 2.8 km offshore along the 30 km strip, and is probably constrained by lateral geo-facial changes.     

High performance liquid chromatographic detection of a strongly retained pigment fraction in Capsicum annuum

A new colour pigment fraction was detected in Capsicum annuum by high performance liquid chromatography. Surprisingly the pigment was strongly bound both to silica and octadecylsilica surfaces indicating that its molecular mass is probably high. Peak purity tests proved that the fraction is not homogeneous and the degree of inhomogeneity depends on the wavelength used for the peak purity test. The spectra taken at one minute intervals of the peak were strikingly different supporting the above conclusions. It is possible that this highly lipophilic pigment is a secondary product of the ripening and processing procedures and is a mixture of individual pigments covalently bound to each other.     

Engineering model of a passive planar air breathing fuel cell cathode

The behavior of an air breathing fuel cell (ABFC) operated on dry-hydrogen in dead-ended mode is studied using theoretical analysis. A one-dimensional, non-isothermal, combined heat and mass transport model is developed that captures the coupling between water generation, oxygen consumption, self-heating and natural convection at the air breathing cathode. The model is validated against planar ABFC experimental measurements over a range of ambient temperatures. The model confirms the strong effect of self-heating on the water balance within passive ABFCs. Model analysis provides several conclusions: (1) thermal runaway caused by inadequate heat rejection predominantly limits ABFC performance. (2) The natural convection boundary layer represents a significant barrier to cathode mass and heat transfer. (3) Because the mass and heat transport numbers associated with natural convection are small, even slight forced convection dramatically affects cell behavior. (4) Performance optimization requires maximizing heat rejection while minimizing flooding. Decoupling the latter two phenomena is challenging due to the exponential relationship between water vapor saturation and temperature.