Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol^–1 min^–1, which is significantly higher than for related Y₅(-O)(O ⁱ Pr)_13– or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.     

Mapping Land-Cover and Mangrove Structures with Remote Sensing Techniques: A Contribution to a Synoptic GIS in Support of Coastal Management in North Brazil

This article deals with the development and application of a cartographic database for a synoptic Geographic Information System (GIS). Its purpose is the storage and evaluation of the heterogeneous datasets of the interdisciplinary scientific research program MADAM (Mangrove Dynamics and Management), which aims to develop recommendations for a tailored integrated coastal management scheme for the mangrove ecosystem at Bragança (North Brazil). The article describes the integration of remote sensing data, aerial photographs, as well as point data provided by fieldwork from different scientific fields. Using various innovative processing techniques and different scale-resolution levels, an assessment of temporal–spatial changes of the mangrove peninsula and the adjacent rural socioeconomic impact area, the type of mangrove structure, as well as a land-use cover analyses was undertaken. The definition of the spatial level of detail was found to be a major issue in the development of the GIS, as well as during the processing and analysis procedures. A division between strong and weak patterns in the mangrove ecosystem could be made, which implies different management measures and sets of specific interdisciplinary studies and monitoring at hierarchical scales.     

Metal Leachability and Anthropogenic Signal in Roadside Soils Estimated from Sequential Extraction and Stable Lead Isotopes

Several roadside soil samples were collected at two field sites in Sweden. They were analysed for total elemental content (using both ICP-MS and XRF) and stable lead isotopes. Extraction with deicing salt solution and sequential extraction were performed in order to elucidate the potential mobility due to the use of deicing agents. The total concentrations of elements, especially lead, have decreased and lead is presently almost at background concentrations (15-51 ppm for surface samples). However, the isotopic signature indicates that old gasoline lead still is left at the site constructed prior to 1975. The field site constructed in 1992 showed, however, no 206Pb/207Pb ratio below 1.14. Only minor amounts were leached using deicing salt solutions; for lead only 0.29%, on average, was extracted indicating that the mobile fraction already was released. Sequential extraction indicated that lead mainly was associated with reducible (34.4%) and oxidisable (35.4%) fractions. Exchangable and acid soluble fractions contained 20.3% while 10.0% was found in the residual fraction. The salt extraction released, however, very low concentrations indicating that most in fraction 1 is acid soluble (e.g. carbonates). Tungsten was also found at high concentrations indicating a possible impact from studded tires. For tungsten the following composition was obtained: residual (48.0%) > oxidisable (47.6%) > reducible (3.3%) > exchangeable/acid soluble (1.1%). From the isotopic studies it was also suggested that the order for incorporating anthropogenic lead into soils is exchangeable/carbonates > (hydr)oxides > organic matter > residual. The multivariate technique principal component analysis (PCA) seems promising for evaluating large sequential extraction datasets.     

Conclusions on plutonium separation from atmospheric krypton-85 measured at various distances from the Karlsruhe reprocessing plant

For wide-area atmospheric monitoring, krypton-85 is the best indicator for clandestine plutonium separations. The detection and false alarm rates were determined from weekly samples at five different distances from the Karlsruhe reprocessing plant between 1985 and 1988. The detection rate for the separation of 4 kg of plutonium per week was found to be as high as 80-90% at a distance of less than 1 km, 70% at 5 km, 40% at 39 km, and 15% at 130 km. At distances up to 40 km, the false alarm rate is less than 3.5%. On average, the fuel released 28 TBq krypton-85 per kg plutonium. For weapons-grade plutonium, the krypton signal would be lower by a factor of 2. Hence, the given percentages correspond to the detection probabilities for the separation of a significant quantity (8 kg) of plutonium per weekly sample under the specific meteorological conditions of the WAK. The minimum separation rates that could have been detected are 2 gram of weapons-grade plutonium per week at a distance of less than 1 km, 40 g/week at 5 km, 200 g/week at 39 km, and 1000 g/week at 130 km.     

History and Ethics of Keeping Pets: Comparison with Farm Animals

Perhaps the commonest reasons for the keeping of pets are companionship and as a conduit for affection. Pets are, therefore, being “used” for human ends in much the same way as laboratory or farm animals. So shouldn’t the same arguments apply to the use of pets as to those used in other ways? In accepting the “rights” of farm animals to fully express their natural behavior, one must also accept the “right” of pets to express their intrinsic natural behavior. Dogs kept in houses for most of the day are being kept in an unnatural environment. So are rabbits kept in hutches, and guinea-pigs or birds in cages. These conditions infringe the animals’ telos. Dogs are naturally pack animals, so is a dog in isolation being denied its telos? Other actions more deliberately infringe telos and autonomy. Enforced shampooing – or even exercise; hair-cutting of poodles; putting animals in clothes; and tail-docking. If de-beaking of chickens is considered wrong, then the same must be true for tail-docking of dogs. One should also question the ethics of specialist breeding – especially when that results in physiological disadvantages (boxers with breathing troubles). There would appear to be no advantage to the animals in having such health problems and when these are the direct result of the breeders’ desire for specific cosmetic traits, we should question the ethics of the practice at least as much as when animals are bred for specific agricultural traits.     

Sustainable development of food production: a case study on scenarios for pig production

To study future, sustainable production systems, a step-wise method was used to create three future scenarios for pig production based on different sustainability goals. The first scenario focused on animal welfare and the natural behavior of the animals. The second targeted low impacts on the environment and the efficient use of natural resources. The third scenario aimed at product quality and safety. Each scenario fulfilled different aspects of sustainability, but there were goal conflicts because no scenario fulfilled all sustainability goals. The scenarios were then parameterized. The environmental impact was calculated using the life-cycle assessment (LCA) methodology, and the economic cost was calculated from the same data set. The cost per kilo of pork was highest for the animal welfare scenario and similar for the other two scenarios. The environmental scenario had the lowest environmental impact, and the product-quality scenario the highest. The results are discussed based on different future priorities.     

Welches sind die existentiellen Grundlagen lebender Systeme?

Biology is searching for a paradigm of life and is proceeding from an inductive, empirical to a deductive, formal science. All life phenomena result from the efficacy of a principle, i.e., systemic information, which is not reducible to physics and chemistry. Systemic information, together with genetic information engraved on macromolecules and matter described by physics and chemistry, represents the existential basis of life. A strategy is developed which makes it possible to determine the systemic information of a living organism provided there is enough knowledge of the organism concerned.     

Rotifers colonising sediments with shallow gas hydrates

Rotifers, one of the smallest metazoans, are only seldom found in marine environments. Surprisingly, we discovered high abundances of at least two new species of rotifers settling in anoxic and highly sulphidic sediments associated with shallow gas hydrates (GH) at the southern crest of Hydrate Ridge off Oregon, NE Pacific, in a water depth of about 780 m. At basins adjacent to Hydrate Ridge, 1,285–2,304 m deep, we found rotifers co-occurring with the sulphide-oxidising bacteria Thioploca sp.     

Potential Remobilization of Toxic Anions during Reduction of Arsenated and Chromated Schwertmannite by the Dissimilatory Fe(III)-Reducing Bacterium Acidiphilium cryptum JF-5

Schwertmannite, an iron(III)-oxyhydroxysulfate formed in acidic mining-impacted stream or lake waters often contaminated with toxic elements like arsenate or chromate, is able to incorporate high amounts of these oxyanions. Detoxification of the water might be achieved if precipitated arsenated or chromated schwertmannite is fixed in the sediment. However, under reduced conditions, reductive dissolution of iron oxides mediated by the activity of Fe(III)-reducing bacteria might mobilize arsenate and chromate again. In this study, the reduction of synthesized arsenated or chromated schwertmannite by the acidophilic Fe(III)-reducer Acidiphilium cryptum JF-5, isolated from an acidic mining-impacted sediment, was investigated. In TSB medium at pH 2.7 with glucose as electron donor, A. cryptum JF-5 reduced about 10% of the total Fe(III) present in pure synthetic schwertmannite but only 5% of Fe(III) present in arsenated schwertmannite. In contrast to sulfate that was released during the reductive dissolution of pure schwertmannite, arsenate was not released during the reduction of arsenated schwertmannite probably due to the high surface complexation constant of arsenate and Fe(III). In medium containing chromated schwertmannite, no Fe(II) was formed, and no glucose was consumed indicating that chromate might have been toxic to cells of A. cryptum JF-5. Both As(V) or Cr(VI) could not be utilized as electron acceptor by A. cryptum JF-5. A comparison between autoclaved (121 °C for 20 min) and non-autoclaved schwertmannite samples demonstrated that nearly 100%of the bound sulfate was released during heating, and FTIR spectra indicated a transformation of schwertmannite to goethite. This structural change was not observed with autoclaved arsenated or chromated schwertmannite. These results suggest that the mobility of arsenate and chromate is not enhanced by the activity of acidophilic Fe(III)-reducing bacteria in mining-impacted sediments. In contrast, the presence of bound arsenate and chromate seemed to stabilize schwertmannite against reductive dissolution and its further transformation to goethite that is an ongoing process in those sediments.