Thermal Conversion of Guanylurea Dicyanamide into Graphitic Carbon Nitride via Prototype CNx Precursors

Guanylurea dicyanamide, [(H2N)C(-O)NHC(NH2)2][N(CN)2], has been synthesized by ion exchange reaction in aqueous solution and structurally characterized by single-crystal X-ray diffraction (C2/c, a = 2249.0(5) pm, b = 483.9(1) pm, c = 1382.4(3) pm, β = 99.49(3)°, V = 1483.8(5) × 106 pm3, T = 130 K). The thermal behavior of the molecular salt has been studied by thermal analysis, temperature-programmed X-ray powder diffraction, FTIR spectroscopy, and mass spectrometry between room temperature and 823 K. The results were interpreted on a molecular level in terms of a sequence of thermally induced addition, cyclization, and elimination reactions. As a consequence, melamine (2,4,6-triamino-1,3,5-triazine) is formed with concomitant loss of HNCO. Further condensation of melamine yields the prototypic CNx precursor melem (2,6,10-triamino-s-heptazine, C6N7(NH2)3), which alongside varying amounts of directly formed CNxHy material transforms into layered CNxHy phases without significant integration of oxygen into the core framework owing to the evaporation of HNCO. Thus, further evidence can be added to melamine and its condensation product melem acting as “key intermediates” in the synthetic pathway toward graphitic CNxHy materials, whose exact constitution is still a point at issue. Due to the characteristic formation process and hydrogen content a close relationship with the polymer melon is evident. In particular, the thermal transformation of guanylurea dicyanamide clearly demonstrates that the formation of volatile compounds such as HNCO during thermal decomposition may render a large variety of previously not considered molecular compounds suitable CNx precursors despite the presence of oxygen in the starting material

Ultrafast polychromatic ionization of dielectric solids

The modeling of the laser-induced damage processes can be divided into thermal and electronic processes. Especially, electronic damage seems to be well understood. In corresponding models, the damage threshold is linked to the excitation of valence electrons into the conduction band, and often the damage is obtained if a critical density of free electrons is exceeded. For the modeling of the electronic excitation, rate equation models are applied which can vary in the different terms representing different excitation channels. According to the current state of the art, photoionization and avalanche ionization contribute the major part to the ionization process, and consequently the determination of laser-induced damage thresholds is based on the calculation of the respective terms. For the theoretical description of both, well established models are available. For the quantitative calculation of the photoionization, the Keldysh theory is used most frequently, and for the avalanche processes the Drude theory is often applied. Both, Drude and Keldysh theory calculations depend on the laser frequency and use a monochromatic approach. For most applications the monochromatic description matches very well with the experimental findings, but in the range of few-cycle pulses the necessary broadening of the laser emission spectrum leads to high uncertainty for the calculation. In this paper, a novel polychromatic approach is presented including photo-and avalanche ionization as well as the critical electron density. The simulation combines different ionization channels in a Monte-Carlo procedure according to the frequency distribution of the spectrum. The resulting influence on the wavelength and material dependency is discussed in detail for various pulse shapes and pulse durations. The main focus of the investigation is concentrated on the specific characteristics in the dispersion and material dependency of the laser-induced damage threshold respecting the polychromatic characteristics of the ultra-short pulse (USP) laser damage. © 2016 SPIE. Downloading of the abstract is permitted for personal use only.Ministry for Science and Culture of Lower SaxonyVolkswagen Stiftun

Phylogenetic Signals of Salinity and Season in Bacterial Community Composition Across the Salinity Gradient of the Baltic Sea

Understanding the key processes that control bacterial community composition has enabled predictions of bacterial distribution and function within ecosystems. In this study, we used the Baltic Sea as a model system to quantify the phylogenetic signal of salinity and season with respect to bacterioplankton community composition. The abundances of 16S rRNA gene amplicon sequencing reads were analyzed from samples obtained from similar geographic locations in July and February along a brackish to marine salinity gradient in the Baltic Sea. While there was no distinct pattern of bacterial richness at different salinities, the number of bacterial phylotypes in winter was significantly higher than in summer. Bacterial community composition in brackish vs. marine conditions, and in July vs. February was significantly different. Non-metric multidimensional scaling showed that bacterial community composition was primarily separated according to salinity and secondly according to seasonal differences at all taxonomic ranks tested. Similarly, quantitative phylogenetic clustering implicated a phylogenetic signal for both salinity and seasonality. Our results support that global patterns of bacterial community composition with respect to salinity and season are the result of phylogenetically clustered ecological preferences with stronger imprints from salinity

Impact of a Major Inflow Event on the Composition and Distribution of Bacterioplankton Communities in the Baltic Sea

Major Baltic inflow (MBI) events carry highly saline water from the North Sea to the central Baltic Sea and thereby affect both its environmental conditions and its biota. While bacterioplankton communities in the Baltic Sea are strongly structured by salinity, how MBIs impact the composition and distribution of bacteria is unknown. The exceptional MBI in 2014, which brought saline and oxygenated water into the basins of the central Baltic Sea, enabled the linkage of microbiological investigations to hydrographic and modeling studies of this MBI. Using sequence data of 16S ribosomal RNA (rRNA) and 16S rRNA genes (rDNA), we analyzed bacterioplankton community composition in the inflowing water and in the uplifted former bottomwater at stations reached by the MBI. Bacterial diversity data were compared with respective data obtained from previous, non-inflow conditions. Changes in bacterial community composition following the 2014 MBI were mainly apparent at the genus level. A number of specific taxa were enriched in the inflowing water, with large changes in the rRNA/rDNA ratios indicating the different activity levels between of the water masses. The relative similarity of the bacterial communities in the inflowing and uplifted waters as well as the results from an inflow-simulating numerical model showed that the inflowing water did not originate directly from the North Sea but mostly from adjacent areas in the Baltic Sea. This suggested that the inflow event led to a series of shifts in Baltic Sea water masses among the Baltic Sea basins and a gradual mixing of the water bodies. Dramatic changes in the bacterial community composition occurred when the bottomwater inflow reached the anoxic, sulfidic deep basins, resulting in an uplifting of the formerly anoxic bacterial community, dominated by Epsilonproteobacteria. Our study of the impact of MBIs on bacterioplankton communities therefore highlights two relevant underlying mechanisms that impact the distribution and possibly also the activities of planktonic bacteria in the Baltic Sea: (1) the successive dilution of inflowing North Sea water with ambient waters and (2) the uplifting of former bottom-water communities to higher water strata.This work was funded by the Deutsche Forschungsgemeinschaft (DFG) (projects JU367/15-1, JU367/16-1 to KJ and LA1466/8- 1 to ML). DH was supported by the European Regional Development Fund and the Estonian Research Council Mobilitas Plus Top Researcher grant “MOBTT24.” UG was supported by the BMBF project “Hydrodynamic observations and simulations of munition in the sea,” a subproject of the collaborative project “Environmental monitoring for the delaboration of munitions in the sea” (Grant No. #03F0747C).This work was funded by the Deutsche Forschungsgemeinschaft (DFG) (projects JU367/15-1, JU367/16-1 to KJ and LA1466/8- 1 to ML). DH was supported by the European Regional Development Fund and the Estonian Research Council Mobilitas Plus Top Researcher grant “MOBTT24.” UG was supported by the BMBF project “Hydrodynamic observations and simulations of munition in the sea,” a subproject of the collaborative project “Environmental monitoring for the delaboration of munitions in the sea” (Grant No. #03F0747C)

Laien und Experten während der ersten Medienrevolution. Transformation der christlichen Wissensordnung in der frühen und späteren Reformation

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Sequence-specific long range networks in PSD-95/discs large/ZO-1 (PDZ) domains tune their binding selectivity.

Protein-protein interactions mediated by modular protein domains are critical for cell scaffolding, differentiation, signaling, and ultimately, evolution. Given the vast number of ligands competing for binding to a limited number of domain families, it is often puzzling how specificity can be achieved. Selectivity may be modulated by intradomain allostery, whereby a remote residue is energetically connected to the functional binding site via side chain or backbone interactions. Whereas several energetic pathways, which could mediate intradomain allostery, have been predicted in modular protein domains, there is a paucity of experimental data to validate their existence and roles. Here, we have identified such functional energetic networks in one of the most common protein-protein interaction modules, the PDZ domain. We used double mutant cycles involving site-directed mutagenesis of both the PDZ domain and the peptide ligand, in conjunction with kinetics to capture the fine energetic details of the networks involved in peptide recognition. We performed the analysis on two homologous PDZ-ligand complexes and found that the energetically coupled residues differ for these two complexes. This result demonstrates that amino acid sequence rather than topology dictates the allosteric pathways. Furthermore, our data support a mechanism whereby the whole domain and not only the binding pocket is optimized for a specific ligand. Such cross-talk between binding sites and remote residues may be used to fine tune target selectivity

More Attacks and Analgesic Use in Old Age: Self-Reported Headache Across the Lifespan in a German Sample

Background: Reliable population-based data on the prevalence and characteristics of primary headache across the lifespan are essential. However, robust data are lacking. Methods: We utilized questionnaire data from a random general population sample in Germany, that comprised 2,478 participants aged ≥14 years. A standardized questionnaire addressing headache and headache treatment was filled in during the face-to-face survey. Results: The 6-month prevalence of self-reported headache in the total sample amounted to 39.0% (known diagnosis of migraine 7.2%; tension-type headache 12.4%; another diagnosis or unknown diagnosis 23.4%). Age-specific prevalence rates were 37.9% (14-34 years), 44.6% (35-54 years), 38.5% (55-74 years), and 26.9% (≥75 years). Compared to age group 14-34, participants aged 35-54 were more (OR = 1.29, 95%-CI 1.05-1.60, p = 0.018) and those aged ≥75 were less (OR = 0.55, 95%-CI 0.40-0.76, p 14 days per month. The frequency of headache did not differ significantly between age groups in men [χ2(3, N = 384) = 1.45, p > 0.05], but in women [χ2(3, N = 651) = 21.57, p 14 days per month: 1.8 (14-34 years), 2.5 (35-54 years), 3.2 (55-74 years), and 3.4 (≥75 years), respectively 7.9 (14-34 years), 11.4 (35-54 years), 18.4 (55-74 years), and 22.8 (≥75 years). Conclusions: In general, the prevalence of headache decreases with age. However, older women suffer from more frequent attacks and older participants take analgesics on more days per month than younger participants. This might put them at risk of medication overuse which may lead to medication overuse headache. More research is needed to understand these specifics in headache frequency and treatment behavior in older people