On-Surface Synthesis of BN-Substituted Heteroaromatic Networks

We report on the bottom-up fabrication of BN-substituted heteroaromatic networks achieved by surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed BN-substituted precursor monomers based on a borazine core structural element. To get insight into the cyclodehydrogenation pathway and the influence of molecular flexibility on network quality, two closely related precursor monomers with different degrees of internal cyclodehydrogenation have been employed. Scanning tunneling microscopy shows that, for both monomers, surface-assisted cyclodehydrogenation allows for complete monomer cyclization and the formation of covalently interlinked BN-substituted polyaromatic hydrocarbon networks on the Ag(111) surface. In agreement with experimental observations, density functional theory calculations reveal a significantly lower energy barrier for the cyclodehydrogenation of the conformationally more rigid precursor monomer, which is also reflected in a higher degree of long-range order of the obtained heteroaromatic network. Our proof-of-concept study will allow for the fabrication of atomically precise substitution patterns within BNC heterostructures.

Bridged bicyclic peptides as potential drug scaffolds: synthesis, structure, protein binding and stability

Double cyclization of short linear peptides obtained by solid phase peptide synthesis was used to prepare bridged bicyclic peptides (BBPs) corresponding to the topology of bridged bicyclic alkanes such as norbornane. Diastereomeric norbornapeptides were investigated by 1H-NMR, X-ray crystallography and CD spectroscopy and found to represent rigid globular scaffolds stabilized by intramolecular backbone hydrogen bonds with scaffold geometries determined by the chirality of amino acid residues and sharing structural features of β-turns and α-helices. Proteome profiling by capture compound mass spectrometry (CCMS) led to the discovery of the norbornapeptide 27c binding selectively to calmodulin as an example of a BBP protein binder. This and other BBPs showed high stability towards proteolytic degradation in serum.

Element concentration and GDGT fractional abundances of sediment core GeoB3910-2

In dieser Arbeit wurde das Zeitintervall zwischen 20 und 10 ka vor heute einschließlich des Heinrichevent 1 und der Younger Dryas am Kern GeoB 3910-2 neu untersucht. An organischen Parametern, basierend auf der Verteilung von bakteriellen GDGTs, und Elementkonzentrationen wurde eine Rekonstruktion der klimatischen Bedingungen und Veränderungen im Hinterland von NO Brasilien durchgeführt. Es zeigt sich, dass sich die durchschnittliche Landtemperatur gleich der Oberflächenwassertemperatur verhält und im Gegensatz zu den Phasen von H6 bis H2 dem antarktischen Erwärmungstrend ab 17 ka vor heute folgt. Weiterhin konnte gezeigt werden, dass durch die südwärts Verlagerung der ITCZ während H1 und der YD die Niederschläge in NO Brasilen intensiviert wurden, was eine Ausbreitung der Flüsse und Änderung der Erosionsgebiete zur Folge hatte.

Physico-chemical characteristics and ikaite content of brine and ice samples taken during SIPEX and DDU campaigns in East Antarctica, 2007

Calcium carbonate precipitation in sea ice is thought to potentially drive significant CO2 uptake by the ocean. However, little is known about the quantitative spatial and temporal distribution of CaCO3 within sea ice, although it is hypothesized that high quantities of dissolved organic matter and/or phosphate (common in sea ice) may inhibit its formation. In this quantitative study of hydrous calcium carbonate as ikaite, sea ice cores and brine samples were collected from pack and land fast sea ice between September and December 2007 during two expeditions, one in the East Antarctic sector and the other off Terre Adélie. Samples were analysed for CaCO3, salinity, dissolved organic carbon/nitrogen, inorganic phosphate, and total alkalinity. No relationship between these parameters and CaCO3 precipitation was evident. Ikaite was found mostly in the uppermost layers of sea ice with maximum concentrations of up to 126 mg ikaite per litre melted sea ice being measured, although both the temporal and horizontal spatial distributions of ikaite were highly heterogeneous. The precipitate was also found in the snow on top of the sea ice at some of the sampling locations.

Temperature, salinity and ikaite crystal characteristics in snow, slush and sea ice during R/V Lance cruise in April-May 2011

We identified ikaite crystals (CaCO3 · 6H2O) and examined their shape and size distribution in first-year Arctic pack ice, overlying snow and slush layers during the spring melt onset north of Svalbard. Additional measurements of total alkalinity (TA) were made for melted snow and sea-ice samples. Ikaite crystals were mainly found in the bottom of the snowpack, in slush and the surface layers of the sea ice where the temperature was generally lower and salinity higher than in the ice below. Image analysis showed that ikaite crystals were characterized by a roughly elliptical shape and a maximum caliper diameter of 201.0±115.9 µm (n = 918). Since the ice-melting season had already started, ikaite crystals may already have begun to dissolve, which might explain the lack of a relationship between ikaite crystal size and sea-ice parameters (temperature, salinity, and thickness of snow and ice). Comparisons of salinity and TA profiles for melted ice samples suggest that the precipitation/dissolution of ikaite crystals occurred at the top of the sea ice and the bottom of the snowpack during ice formation/melting processes.

Onset of long-term cooling of Greenland near the Eocene-Oligocene boundary as revealed by branched tetraether lipids

The Eocene-Oligocene (E-O) boundary interval is considered to be one of the major transitions in Earth's climate, witnessing the first major expansion of the East Antarctic Ice Sheet. However, the extent of the associated climatic cooling, especially for high northern latitude continental landmasses, is poorly constrained. In this study we reconstruct the first mean annual air temperature (MAAT) for the Greenland landmass during the late Eocene and early Oligocene by applying a new proxy based on the distribution of branched tetraether lipids derived from soil bacteria preserved in a marine sediment core from the Greenland Basin. The temperature estimates are compared with a composite continental temperature record based on bio-climatic analysis of pollen assemblages. Both proxies reveal comparable late Eocene MAATs of ~13-15 °C and a gradual long-term cooling of ~3-5 °C starting near the E-O boundary. These data are in agreement with other MAAT reconstructions from northern midlatitude continents and suggest a general cooling of the Northern Hemisphere during the E-O transition.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Fractional abundance and indices for brGDGTs and crenarchaeol in dust samples, surface water samples and surface sediment samples

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'-CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset.