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Am alten Markt
(2012)
alpha,beta-Unsaturated d-lactones are accessible via a sequential ring-closing metathesis (RCM) double-bond migration reaction starting from butenoates of allyl alcohols. This approach proceeds efficiently with lower catalyst loadings and higher initial substrate concentrations compared to the alternative RCM of acrylates derived from homoallylic alcohols.
The ongoing global amphibian decline calls for an increase of habitat and population management efforts. Pond restoration and construction is more and more accompanied by breeding and translocation programs. However, the appropriateness of translocations as a tool for conservation has been widely debated, as it can cause biodiversity loss through genetic homogenization and can disrupt local adaptation, eventually leading to outbreeding depression. In this study, we investigated the genetic structure of two translocated populations of the critically endangered fire-bellied toad Bombina bombina at its north western distribution edge using supposedly neutral genetic markers (variation in the mitochondrial control region and microsatellites) as well as a marker under selection (major histocompatibility complex (MHC) genes). While one of the newly established populations showed the typical genetic composition of surrounding populations, the other was extremely diverged without clear affinity to its putative source. In this population we detected a profound impact of allochthonous individuals: 100% of the analyzed individuals exhibited a highly divergent mitochondrial haplotype which was otherwise found in Austria. 83% of them were also assigned to Austria by the analysis of microsatellites. Interestingly, for the adaptive marker (MHC) local alleles were predominant in this population, while only very few alleles were shared with the Austrian population. Probably Mendelian inheritance has reshuffled genotypes such that adaptive local alleles are maintained (here, MHC), while presumably neutral allochthonous alleles dominate at other loci. The release of allochthonous individuals generally increased the genetic variability of the affected population without wiping out locally adaptive genotypes. Thus, outbreeding depression might be less apparent than sometimes thought and natural selection appears strong enough to maintain locally adaptive alleles, at least in functionally important immune system genes.
The synthesis of block copolymers consisting of poly(vinylidene fluoride) (PVDF) and polystyrene (PS) is reported. Firstly, a propargyl-functionalized alkoxyamine initiator (PgOTIPNO) was prepared and subsequently used for the preparation of a propargyl-terminated PS homopolymer of different chain lengths with low dispersities via nitroxide-mediated radical polymerization. A tailored PVDF homopolymer with iodine end groups originating from iodine transfer polymerization was transformed to PVDF with azide end group. Then, alkyne-terminated PS with different molecular weights and azide-terminated PVDF were joined together via copper-catalyzed alkyne-azide coupling. The block copolymers were characterized using H-1-NMR, F-19-NMR, IR, SEC, and DSC.
The wide knowledge gaps in invasion biology research that exist in the developing world are crucial impediments to the scientific management and global policymaking on biological invasions. In an effort to fill such knowledge gaps, we present here an inventory of the alien flora of India, based on systematic reviews and rigorous analyses of research studies (ca. 190) published over the last 120 years (1890-2010 AD), and updated with field records of the last two decades. Currently, the inventory comprises of 1,599 species, belonging to 842 genera in 161 families, and constitutes 8.5% of the total Indian vascular flora. The three most species-rich families are Asteraceae (134 spp.), Papilionaceae (114 spp.) and Poaceae (106 spp.), and the three largest genera are Eucalyptus (25 spp.), Ipomoea (22 spp.), and Senna (21 spp.). The majority of these species (812) have no report of escaping from cultivation. Of the remaining subset of 787 species, which have either escaped from intentional cultivation, or spread after unintentional introduction, casuals are represented by 57 spp., casual/naturalised by 114 spp., naturalised by 257 spp., naturalised/invasive by 134 spp., and invasive by 225 spp. Biogeographically, more than one-third (35%) of the alien flora in India has its native ranges in South America, followed by Asia (21%), Africa (20%), Europe (11%), Australia (8%), North America (4%); and cryptogenic (1%). The inventory is expected to serve as the scientific baseline on plant invasions in India, with implications for conservation of global biodiversity.
Daniel Kehlmanns Roman „Die Vermessung der Welt“ wird hoch gepriesen und streng kritisiert. Kehlmanns Kritiker lesen seine Satire als eine verfälschte Biographie von Gauss und Humboldt, obwohl der Autor wiederholt selbstironische Bemerkungen eingestreut hat, die sein wahres Ziel offenbaren. Der Aufsatz bemüht sich, Kehlmanns fiktiven Roman angemessen zu beurteilen und einige der wirklichen Aktivitäten und Errungenschaften von Gauss und Humboldt zu charakterisieren, indem Kehlmanns erzählte mit den historischen Tatsachen verglichen werden. Beide Wissenschaftler waren stark am Erdmagnetismus interessiert, was zeitweise zu einigen Spannungen zwischen ihnen führte. Humboldts Messmethoden und seine Überzeugung, dass alles Wechselwirkung ist, waren zwei Seiten derselben Medaille. Nur numerische Elemente konnten helfen, die Gesetze zu finden, die die Natur regieren. Humboldts wissenschaftliche Techniken und Ziele (Methode der Mittelwerte) waren gut begründet. Humboldts Reisen und Forschen bildeten eine untrennbare Einheit. Humboldts Naturbegriff schloss beide Möglichkeiten ein, das heißt die natura naturans und die natura naturata, die schaffende und herrschende Natur und die Natur, die von bestimmten Gesetzen beherrscht war. Sein überragendes Interesse an Naturgesetzen gründete auf der Überzeugung, dass sie ewig waren und dass sie die Ordnung und Ewigkeit der Welt garantierten.
Wie stark sich im Verlauf des zurückliegenden Vierteljahrhunderts der Bekanntheitsgrad Alexander von Humboldts in der deutschsprachigen Öffentlichkeit verändert hat, zeigen nicht nur Fernsehumfragen zu den berühmtesten Deutschen, in denen Alexander von Humboldt mittlerweile figuriert, oder Fernsehserien, die über aktuelle Expeditionen berichten und auf Humboldts Namen zurückgreifen. Am deutlichsten vielleicht belegt dies der enorme Erfolg von Daniel Kehlmanns Roman Die Vermessung der Welt, der ohne die zuvor skizzierte Entwicklung nicht denkbar gewesen wäre. Es ist vor diesem Hintergrund nicht nur reizvoll, sondern aufschlußreich, sich mit dem großen Erfolg dieses kleinen Romans zu beschäftigen. Worum geht es in Die Vermessung der Welt? Und wie läßt sich das »Phänomen Kehlmann« aus etwas größerer Distanz erklären?
We explore the photophysics of P(NDI2OD-T2), a high-mobility and air-stable n-type donor/acceptor polymer. Detailed steady-state UV-vis and photoluminescence (PL) measurements on solutions of P(NDI2OD-T2) reveal distinct signatures of aggregation. By performing quantum chemical calculations, we can assign these spectral features to unaggregated and stacked polymer chains. NMR measurements independently confirm the aggregation phenomena of P(NDI2OD-T2) in solution. The detailed analysis of the optical spectra shows that aggregation is a two-step process with different types of aggregates, which we confirm by time-dependent PL measurements. Analytical ultracentrifugation measurements suggest that aggregation takes place within the single polymer chain upon coiling. By transferring these results to thin P(NDI2OD-T2) films, we can conclude that film formation is mainly governed by the chain collapse, leading in general to a high aggregate content of similar to 45%. This process also inhibits the formation of amorphous and disordered P(NDI2OD-T2) films.
Particles in Saturn's main rings range in size from dust to kilometer-sized objects. Their size distribution is thought to be a result of competing accretion and fragmentation processes. While growth is naturally limited in tidal environments, frequent collisions among these objects may contribute to both accretion and fragmentation. As ring particles are primarily made of water ice attractive surface forces like adhesion could significantly influence these processes, finally determining the resulting size distribution. Here, we derive analytic expressions for the specific self-energy Q and related specific break-up energy Q(star) of aggregates. These expressions can be used for any aggregate type composed of monomeric constituents. We compare these expressions to numerical experiments where we create aggregates of various types including: regular packings like the face-centered cubic (fcc), Ballistic Particle Cluster Aggregates (BPCA), and modified BPCAs including e.g. different constituent size distributions. We show that accounting for attractive surface forces such as adhesion a simple approach is able to: (a) generally account for the size dependence of the specific break-up energy for fragmentation to occur reported in the literature, namely the division into "strength" and "gravity" regimes and (b) estimate the maximum aggregate size in a collisional ensemble to be on the order of a few tens of meters, consistent with the maximum particle size observed in Saturn's rings of about 10 m.
On 27 February 2010 the M-w 8.8 Maule earthquake in Central Chile ruptured a seismic gap where significant strain had accumulated since 1835. Shortly after the mainshock a dense network of temporary seismic stations was installed along the whole rupture zone in order to capture the aftershock activity. Here, we present the aftershock distribution and first motion polarity focal mechanisms based on automatic detection algorithms and picking engines. By processing the seismic data between 15 March and 30 September 2010 from stations from IRIS, IPGP, GFZ and University of Liverpool we determined 20,205 hypocentres with magnitudes M-w between 1 and 5.5. Seismic activity occurs in six groups: 1.) Normal faulting outer rise events 2.) A shallow group of plate interface seismicity apparent at 25-35 km depth and 50-120 km distance to the trench with some variations between profiles. Along strike, the aftershocks occur largely within the zone of coseismic slip but extend similar to 50 km further north, and with predominantly shallowly dipping thrust mechanisms. Along dip, the events are either within the zone of coseismic slip, or downdip from it, depending on the coseismic slip model used. 3.) A third band of seismicity is observed further downdip at 40-50 km depth and further inland at 150-160 km trench perpendicular distance, with mostly shallow dipping (similar to 28 degrees) thrust focal mechanisms indicating rupture of the plate interface significantly downdip of the coseismic rupture, and presumably above the intersection of the continental Moho with the plate interface. 4.) A deep group of intermediate depth events between 80 and 120 km depth is present north of 36 degrees S. Within the Maule segment, a large portion of events during the inter-seismic phase originated from this depth range. 5.) The magmatic arc exhibits a small amount of crustal seismicity but does not appear to show significantly enhanced activity after the M-w 8.8 Maule 2010 earthquake. 6.) Pronounced crustal aftershock activity with mainly normal faulting mechanisms is found in the region of Pichilemu (similar to 34.5 degrees S). These crustal events occur in a similar to 30 km wide region with sharp inclined boundaries and oriented oblique to the trench. The best-located events describe a plane dipping to the southwest, consistent with one of the focal planes of the large normal-faulting aftershock (M-w = 6.9) on 11 March 2010.
Microbial communities can subsist at depth in marine sediments without fresh supply of organic matter for millions of years. At threshold sedimentation rates of 1 millimeter per 1000 years, the low rates of microbial community metabolism in the North Pacific Gyre allow sediments to remain oxygenated tens of meters below the sea floor. We found that the oxygen respiration rates dropped from 10 micromoles of O-2 liter(-1) year(-1) near the sediment-water interface to 0.001 micromoles of O-2 liter(-1) year(-1) at 30-meter depth within 86 million-year-old sediment. The cell-specific respiration rate decreased with depth but stabilized at around 10(-3) femtomoles of O-2 cell(-1) day(-1) 10 meters below the seafloor. This result indicated that the community size is controlled by the rate of carbon oxidation and thereby by the low available energy flux.
We propose a simple theoretical model for aggregative and fragmentative collisions in Saturn's dense rings. In this model the ring matter consists of a bimodal size distribution: large (meter sized) boulders and a population of smaller particles (tens of centimeters down to dust). The small particles can adhesively stick to the boulders and can be released as debris in binary collisions of their carriers. To quantify the adhesion force we use the JKR theory (Johnson, K., Kendall, K., Roberts, A. [1971]. Proc. R. Soc. Lond. A 324, 301-313). The rates of release and adsorption of particles are calculated, depending on material parameters, sizes, and plausible velocity dispersions of carriers and debris particles. In steady state we obtain an expression for the amount of free debris relative to the fraction still attached to the carriers. In terms of this conceptually simple model a paucity of subcentimeter particles in Saturn's rings (French, R.G., Nicholson, P.D. [2000]. Icarus 145, 502-523; Marouf, E. et al. [2008]. Abstracts for "Saturn after Cassini-Huygens" Symposium, Imperial College London, UK, July 28 to August 1, p. 113) can be understood as a consequence of the increasing strength of adhesion (relative to inertial forces) for decreasing particle size. In this case particles smaller than a certain critical radius remain tightly attached to the surfaces of larger boulders, even when the boulders collide at their typical speed. Furthermore, we find that already a mildly increased velocity dispersion of the carrier-particles may significantly enhance the fraction of free debris particles, in this way increasing the optical depth of the system.
Terrestrial mud volcanoes (TMVs) represent geochemically diverse habitats with varying sulfur sources and yet sulfur cycling in these environments remains largely unexplored. Here we characterized the sulfur-metabolizing microorganisms and activity in four TMVs in Azerbaijan. A combination of geochemical analyses, biological rate measurements and molecular diversity surveys (targeting metabolic genes aprA and dsrA and SSU ribosomal RNA) supported the presence of active sulfur-oxidizing and sulfate-reducing guilds in all four TMVs across a range of physiochemical conditions, with diversity of these guilds being unique to each TMV. The TMVs varied in potential sulfate reduction rates (SRR) by up to four orders of magnitude with highest SRR observed in sediments where in situ sulfate concentrations were highest. Maximum temperatures at which SRR were measured was 60 degrees C in two TMVs. Corresponding with these trends in SRR, members of the potentially thermophilic, spore-forming, Desulfotomaculum were detected in these TMVs by targeted 16S rRNA analysis. Additional sulfate-reducing bacterial lineages included members of the Desulfobacteraceae and Desulfobulbaceae detected by aprA and dsrA analyses and likely contributing to the mesophilic SRR measured. Phylotypes affiliated with sulfide-oxidizing Gamma- and Betaproteobacteria were abundant in aprA libraries from low sulfate TMVs, while the highest sulfate TMV harboured 16S rRNA phylotypes associated with sulfur-oxidizing Epsilonproteobacteria. Altogether, the biogeochemical and microbiological data indicate these unique terrestrial habitats support diverse active sulfur-cycling microorganisms reflecting the in situ geochemical environment.
Although the positive effect of elevated CO2 concentration [CO2] on plant growth is well known, it remains unclear whether global climate change will positively or negatively affect crop yields. In particular, relatively little is known about the role of hormone pathways in controlling the growth responses to elevated [CO2]. Here, we studied the impact of elevated [CO2] on plant biomass and metabolism in Arabidopsis (Arabidopsis thaliana) in relation to the availability of gibberellins (GAs). Inhibition of growth by the GA biosynthesis inhibitor paclobutrazol (PAC) at ambient [CO2] (350 mu mol CO2 mol(-1)) was reverted by elevated [CO2] (750 mu mol CO2 mol(-1)). Thus, we investigated the metabolic adjustment and modulation of gene expression in response to changes in growth of plants imposed by varying the GA regime in ambient and elevated [CO2]. In the presence of PAC (low-GA regime), the activities of enzymes involved in photosynthesis and inorganic nitrogen assimilation were markedly increased at elevated [CO2], whereas the activities of enzymes of organic acid metabolism were decreased. Under ambient [CO2], nitrate, amino acids, and protein accumulated upon PAC treatment; however, this was not the case when plants were grown at elevated [CO2]. These results suggest that only under ambient [CO2] is GA required for the integration of carbohydrate and nitrogen metabolism underlying optimal biomass determination. Our results have implications concerning the action of the Green Revolution genes in future environmental conditions.
We present a momentum transfer mechanism mediated by electromagnetic fields that originates in a system of two nearby molecules: one excited (donor D*) and the other in ground state (acceptor A). An intermolecular force related to fluorescence resonant energy or Forster transfer (FRET) arises in the unstable D* A molecular system, which differs from the equilibrium van der Waals interaction. Due to the its finite lifetime, a mechanical impulse is imparted to the relative motion in the system. We analyze the FRET impulse when the molecules are embedded in free space and find that its magnitude can be much greater than the single recoil photon momentum, getting comparable with the thermal momentum (Maxwell-Boltzmann distribution) at room temperature. In addition, we propose that this FRET impulse can be exploited in the generation of acoustic waves inside a film containing layers of donor and acceptor molecules, when a picosecond laser pulse excites the donors. This acoustic transient is distinguishable from that produced by thermal stress due to laser absorption, and may therefore play a role in photoacoustic spectroscopy. The effect can be seen as exciting a vibrating system like a string or organ pipe with light; it may be used as an opto-mechanical transducer.
Information integration across company borders becomes increasingly important for the success of product lifecycle management in industry and complex supply chains. Semantic technologies are about to play a crucial role in this integrative process. However, cross-company data exchange requires mechanisms to enable fine-grained access control definition and enforcement, preventing unauthorized leakage of confidential data across company borders. Currently available semantic repositories are not sufficiently equipped to satisfy this important requirement. This paper presents an infrastructure for controlled sharing of semantic data between cooperating business partners. First, we motivate the need for access control in semantic data federations by a case study in the industrial service sector. Furthermore, we present an architecture for controlling access to semantic repositories that is based on our newly developed SemForce security service. Finally, we show the practical feasibility of this architecture by an implementation and several performance experiments.
We investigate the physical state of H?i absorbing gas at low redshift (z = 0.25) using a subset of cosmological, hydrodynamic simulations from the OverWhelmingly Large Simulations project, focusing in particular on broad (bHI=40 km s-1) H?i Lya absorbers (BLAs), which are believed to originate in shock-heated gas in the warm-hot intergalactic medium (WHIM). Our fiducial model, which includes radiative cooling by heavy elements and feedback by supernovae and active galactic nuclei, predicts that by z = 0.25 nearly 60?per cent of the gas mass ends up at densities and temperatures characteristic of the WHIM and we find that half of this fraction is due to outflows. The standard H?i observables (distribution of H?i column densities NH?I, distribution of Doppler parameters bHI, bHINH?I correlation) and the BLA line number density predicted by our simulations are in remarkably good agreement with observations. BLAs arise in gas that is hotter, more highly ionized and more enriched than the gas giving rise to typical Lya forest absorbers. The majority of the BLAs arise in warm-hot [log?(T/?K) similar to 5] gas at low (log?? < 1.5) overdensities. On average, thermal broadening accounts for at least 60?per cent of the BLA linewidth, which in turn can be used as a rough indicator of the thermal state of the gas. Detectable BLAs account for only a small fraction of the true baryon content of the WHIM at low redshift. In order to detect the bulk of the mass in this gas phase, a sensitivity at least one order of magnitude better than achieved by current ultraviolet spectrographs is required. We argue that BLAs mostly trace gas that has been shock heated and enriched by outflows and that they therefore provide an important window on a poorly understood feedback process.