First-Principles Study of Elastic Constants and Interlayer Interactions of Complex Hydrated Oxides: Case Study of Tobermorite and Jennite

It is a common perception that layered materials are soft in the interlayer direction. Herein, we present results of first-principles calculations of the structure and elastic constants of a class for hydrated oxides, tobermorite, and jennite, which illustrate that this is not the case, if (1) the interlayer distance is such that coulombic interlayer interactions become comparable to the iono-covalent intralayer interactions and (2) the existence of interlayer ions and water molecules do not shield the coulombic interlayer interactions. In this case, the mechanically softest directions are two inclined regions that form a hinge mechanism. The investigated class of materials and results are relevant to chemically complex hydrated oxides such as layered calcium–silicate–hydrates (C–S–H), the binding phase of all concrete materials, and the principle source of their strength and stiffness. In addition, the first-principles results may serve as a benchmark for validating empirical force fields required for the analysis of complex calcio–silicate oxides.     

A Peroxygenase from Chaetomium globosum Catalyzes the Selective Oxygenation of Testosterone

Unspecific peroxygenases (UPO, EC 1.11.2.1) secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less‐activated hydrocarbons, by transferring peroxide‐borne oxygen. We investigated a cell‐free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg^?1. Although the well‐known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5‐epoxide of testosterone in β‐configuration and 16α‐hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules.     

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.     

Fe-Zeolite as on-Site Regenerable Adsorber for Chlorohydrocarbons in Groundwater – from Laboratory to Pilot Test

This study describes the design and upscaling of an on-site regenerable adsorbent fixed bed of Fe-loaded MFI zeolite for removal of chlorinated hydrocarbons (CHCs) from contaminated groundwater from laboratory studies to pilot scale. The zeolite has an excellent adsorption performance for the hydrophilic CHCs and can be regenerated on-site by flushing with H₂O₂ to degrade adsorbed contaminants by a catalytic Fenton-like reaction. In the pilot test, the Fe-zeolite (30 kg) maintained its performance over treatment of 1470 m³ of groundwater in 12 adsorption/regeneration cycles.     

Tagging Glycoproteins with Fluorescently Labeled GDP‐Fucoses by Using α1,3‐Fucosyltransferases

Fucose‐containing glycans mediate a variety of biological processes, but there is little information on reaction processes and mechanisms mediated by fucosyltransferases. We recently reported on fluorescently labeled GDP‐β‐L ‐fucose‐ATTO 550, which enabled monitoring of α1,3‐fucosyltransferase activity. Here we present an extension to the previously described results, based on the synthesis of a fluorescein‐isothiocyanate (FITC)‐labeled and two carboxyfluorescein‐labeled (FAM‐labeled) NDP‐β‐L ‐fucose derivatives, and applied all four compounds in labeling of different glycoproteins with the aid of four different fucosyltransferases. The labeling processes were analyzed by in‐gel fluorescence and fluorescence polarization measurements. Comparison with the ATTO‐labeled sugar revealed that the FITC‐labeled fucose was the best of these substrates, and that the bacterial enzyme HP‐FucT tolerated the fluorescent substrates better than human fucosyltransferases.     

Blends of thermoplastic polyurethane and maleic-anhydride grafted polyethylene. I: Morphology and mechanical properties

Thermoplastic polyurethane elastomers (TPU) and polyethylene (PE) form immiscible blends with an extremely low compatibility. In order to improve the dispersion, stability, and properties of these blends, polyethylene was grafted with maleic anhydride (PE-g-MA). Subsequently, it was blended with a commercial polyester - type TPU in a twin-screw extruder. With PE-g-MA as blend component, the particle size was dramatically reduced in comparison with PE. Coalescence was significantly reduced and the increase in particle size with composition was less pronounced than in blends with PE. In addition, the phase adhesion and the mechanical properties were improved by using PE-g-MA as minor component. Grafting of the MA onto the PE leads to a decrease of the molecular weight, the melt viscosity, and the mechanical properties of the pure PE. Hence, the reactive blend system exhibits a lower viscosity ratio. Comparison of these results with those from uncompatibilized blends with different viscosity ratios revealed that the reduction in viscosity ratio has a big influence on the blend morphology and because of that on the mechanical properties. In addition, there is a further effect on morphology and properties caused by the reduction in interfacial tension, which results from the compatibilizer formed at the interface.     

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 °N-82 °N) and a temperate marine (Baltic Sea 54 °N-62 °N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB]_org; pg/kg lipid) to the dissolved water concentration (C_w; pg/L). The BAF_Arctic:BAF_Temperate ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF_Arcti:BAF_Temperate) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic.     

Chlorobenzenes, chlorinated pesticides, coplanar chlorobiphenyls and other organochlorine compounds in Greenland biota

This paper summarises the levels and composition of chlorobenzenes, chlorinated pesticides, coplanar polychlorinated biphenyls (PCBs) and the chlorinated compounds octachlorostyrene (OCS), hexachlorocyclobutadiene (HCBD) and pentachloro-anisole (PCA) in biota from the terrestrial, freshwater and marine environment of Greenland. The data were obtained during the second phase of the Arctic Monitoring and Assessment Programme (AMAP). Of the chlorobenzenes, hexachlorobenzene was the main constituent detected in almost all samples. The chlorobenzenes accumulate in the marine food web in a similar manner to the better-studied persistent organic pollutants, with maximum concentrations in beluga, minke whale and narwhal. However, concentrations in ringed seals and kittiwakes were lower than in marine fish, contradicting biomagnification. Of the organochlorine pesticides, the drin pesticides (aldrin, endrin, dieldrin) and heptachlor had increasing concentrations along the food chain, whilst biomagnification was less pronounced for endosulfan, methoxychlor and mirex. Endosulfan and methoxychlor are pesticides still in use and considered less persistent than other organochlorine pesticides. Their occurrence in Arctic biota is of particular concern, also given the high acute toxicity of endosulfan to fish. Chlorobenzene and pesticide concentrations tended to be lower in the Greenland samples than in the same animals from the Canadian Arctic, whilst their concentrations were similar to samples from Svalbard and Iceland. However, temporal trends might overlap the geographical differences. Coplanar chlorobiphenyls (CBs) were found in all samples analysed, with the maximum concentrations found in marine mammals such as beluga and narwhal. Biota from the terrestrial environment appeared to be less contaminated. The main contributor on a TEQ basis was CB126. OCS, HCBD and PCA were detected in biota from Greenland, although at very low concentrations. OCS seems to have the widest occurrence and the highest potential for biomagnification of the three compounds analysed.