High mobility dry-transferred CVD bilayer graphene

We report on the fabrication and characterization of high-quality chemical vapor-deposited (CVD) bilayer graphene (BLG). In particular, we demonstrate that CVD-grown BLG can mechanically be detached from the copper foil by an hexagonal boron nitride (hBN) crystal after oxidation of the copper-to-BLG interface. Confocal Raman spectroscopy reveals an AB-stacking order of the BLG crystals and a high structural quality. From transport measurements on fully encapsulated hBN/BLG/hBN Hall bar devices we extract charge carrier mobilities up to 180,000 cm$^2$/(Vs) at 2 K and up to 40,000 cm$^2$/(Vs) at 300 K, outperforming state-of-the-art CVD bilayer graphene devices. Moreover, we show an on-off ration of more than 10,000 and a band gap opening with values of up to 15 meV for a displacement field of 0.2 V/nm in such CVD grown BLG.Comment: 5 pages, 4 figure

Skin- and Plasmaautofluorescence in hemodialysis with glucose-free or glucose-containing dialysate

Abstract Background Haemodialysis (HD) patients suffer from an increased risk of cardiovascular disease (CVD). Skin autofluorescence (SAF) is a strong marker for CVD. SAF indirectly measures tissue advanced glycation end products (AGE) being cumulative metabolites of oxidative stress and cytokine-driven inflammatory reactions. The dialysates often contain glucose. Methods Autofluorescence of skin and plasma (PAF) were measured in patients on HD during standard treatment (ST) with a glucose-containing dialysate ( n \u2009=\u200924). After that the patients were switched to a glucose-free dialysate (GFD) for a 2-week period. New measurements were performed on PAF and SAF after 1\ua0week (M1) and 2\ua0weeks (M2) using GFD. Nonparametric paired statistical analyses were performed between each two periods. Results SAF after HD increased non-significantly by 1.2% while when a GFD was used during HD at M1, a decrease of SAF by 5.2% ( p \u2009=\u20090.002) was found. One week later (M2) the reduction of 1.6% after the HD was not significant ( p \u2009=\u20090.33). PAF was significantly reduced during all HD sessions. Free and protein-bound PAF decreased similarly whether glucose containing or GFD was used. The HD resulted in a reduction of the total PAF of approximately 15%, the free compound of 20% and the protein bound of 10%. The protein bound part of PAF corresponded to approximately 56% of the total reduction. The protein bound concentrations after each HD showed the lowest value after 2\ua0weeks using glucose-free dialysate ( p \u2009<\u20090.05). The change in SAF could not be related to a change in PAF. Conclusions When changing to a GFD, SAF was reduced by HD indicating that such measure may hamper the accumulation and progression of deposits of AGEs to protein in tissue, and thereby also the development of CVD. Glucose-free dialysate needs further attention. Protein binding seems firm but not irreversible. Trial registration ISRCTN registry: ISRCTN13837553 . Registered 16/11/2016 (retrospectively registered)

Recycling and Assessment of Struvite Phosphorus from Sewage Sludge

AbstractThis study presents an integrated approach for the recovery of P from the wastewater path. Since natural P sources are limited, recycling processes are making an increasingly important contribution to meeting the nutritional requirements of plant production. The groundwork for developing a new fertilizer from upgraded sewage sludge includes an evaluation of nutrients and heavy metal contents. Struvite (NH4MgPO4 • 6 H2O) derived from sewage sludge had a total P content of 6.1% with 3.5% being water-soluble. Plant availability was tested in pot experiments with wheat and maize. P uptake rates were 66.7% and 85.9%, respectively. In terms of heavy metal contents, struvite showed contaminant levels at least three times below the limiting values of the German Sewage Sludge Ordinance. Stricter rules of the German Federal Soil Protection Act are also fulfilled if the loading of heavy metals is considered during periodical fertilization. This implies that P recovery as struvite may be one way of declaring a new type of fertilizer.

YANA – a software tool for analyzing flux modes, gene-expression and enzyme activities

BACKGROUND: A number of algorithms for steady state analysis of metabolic networks have been developed over the years. Of these, Elementary Mode Analysis (EMA) has proven especially useful. Despite its low user-friendliness, METATOOL as a reliable high-performance implementation of the algorithm has been the instrument of choice up to now. As reported here, the analysis of metabolic networks has been improved by an editor and analyzer of metabolic flux modes. Analysis routines for expression levels and the most central, well connected metabolites and their metabolic connections are of particular interest. RESULTS: YANA features a platform-independent, dedicated toolbox for metabolic networks with a graphical user interface to calculate (integrating METATOOL), edit (including support for the SBML format), visualize, centralize, and compare elementary flux modes. Further, YANA calculates expected flux distributions for a given Elementary Mode (EM) activity pattern and vice versa. Moreover, a dissection algorithm, a centralization algorithm, and an average diameter routine can be used to simplify and analyze complex networks. Proteomics or gene expression data give a rough indication of some individual enzyme activities, whereas the complete flux distribution in the network is often not known. As such data are noisy, YANA features a fast evolutionary algorithm (EA) for the prediction of EM activities with minimum error, including alerts for inconsistent experimental data. We offer the possibility to include further known constraints (e.g. growth constraints) in the EA calculation process. The redox metabolism around glutathione reductase serves as an illustration example. All software and documentation are available for download at . CONCLUSION: A graphical toolbox and an editor for METATOOL as well as a series of additional routines for metabolic network analyses constitute a new user-friendly software for such efforts

Structure and bonding of proximity-enforced main-group dimers stabilized by a rigid naphthyridine diimine ligand

The development of ligands capable of effectively stabilizing highly reactive main-group species has led to the experimental realization of a variety of systems with fascinating properties. In this work, we computationally investigate the electronic, structural, energetic, and bonding features of proximity-enforced group 13–15 homodimers stabilized by a rigid expanded pincer ligand based on the 1,8-naphthyridine (napy) core. We show that the redox-active naphthyridine diimine (NDI) ligand enables a wide variety of structural motifs and element-element interaction modes, the latter ranging from isolated, element-centered lone pairs (e.g., E = Si, Ge) to cases where through-space π bonds (E = Pb), element-element multiple bonds (E = P, As) and biradical ground states (E = N) are observed. Our results hint at the feasibility of NDI-E2 species as viable synthetic targets, highlighting the versatility and potential applications of napy-based ligands in main-group chemistry

New cysteine protease inhibitors : electrophilic (het)arenes and unexpected prodrug identification for the trypanosoma protease rhodesain

Electrophilic (het)arenes can undergo reactions with nucleophiles yielding π- or Meisenheimer (σ-) complexes or the products of the SNAr addition/elimination reactions. Such building blocks have only rarely been employed for the design of enzyme inhibitors. Herein, we demonstrate the combination of a peptidic recognition sequence with such electrophilic (het)arenes to generate highly active inhibitors of disease-relevant proteases. We further elucidate an unexpected mode of action for the trypanosomal protease rhodesain using NMR spectroscopy and mass spectrometry, enzyme kinetics and various types of simulations. After hydrolysis of an ester function in the recognition sequence of a weakly active prodrug inhibitor, the liberated carboxylic acid represents a highly potent inhibitor of rhodesain (Ki = 4.0 nM). The simulations indicate that, after the cleavage of the ester, the carboxylic acid leaves the active site and re-binds to the enzyme in an orientation that allows the formation of a very stable π-complex between the catalytic dyad (Cys-25/His-162) of rhodesain and the electrophilic aromatic moiety. The reversible inhibition mode results because the SNAr reaction, which is found in an alkaline solvent containing a low molecular weight thiol, is hindered within the enzyme due to the presence of the positively charged imidazolium ring of His-162. Comparisons between measured and calculated NMR shifts support this interpretation

Das Dimethylbismut-Kation: Zugang zu dativen Bi-Bi-Bindungen und unkonventionellem Methylaustausch

Die Isolierung einfacher, hochreaktiver metallorganischer Verbindungen von grundlegendem Interesse gehört nach wie vor zu den schwierigsten Aufgaben in der Synthesechemie. Die detaillierte Charakterisierung solcher Verbindungen ist der Schlüssel zum Verständnis neuer Bindungsszenarien und Reaktivitäten. Das Dimethylbismut-Kation, [BiMe2(SbF6)] (1), wurde isoliert und charakterisiert. Seine Reaktion mit BiMe3 ermöglicht den Zugang zu einer bislang unbekannten dativen Bindung, der Bi→Bi-Donor/Akzeptor-Wechselwirkung. Der Austausch von Methylgruppen (der wohl einfachsten Kohlenwasserstoffeinheit) zwischen verschiedenen Metallatomen gehört zu den wichtigsten Reaktionstypen in der metallorganischen Chemie. Die Reaktion von 1 mit BiMe3 ermöglicht einen Methylaustausch über eine Rückseiten-SE2-Reaktion, welche zum ersten Mal im Detail für isolierbare, (pseudo-)homoleptische Hauptgruppenverbindungen untersucht wird

Diborane(4) Azides: Surprisingly Stable Sources of Transient Iminoboranes

Herein we describe the first examples of isolable electron-precise diboranes(4) that bear azide moieties: the acyclic 1,2-diazido-1,2-bis(dimethylamino)diborane(4) and the cyclic 1,4-diaryl-2,3-diazido-1,4-diaza-2,3-diborinines (aryl=mesityl, 2,6-xylyl, 4-tolyl). The reported examples are not only stable enough to be observed and isolated (putative transient diborane(4) azides previously reported by our group spontaneously decompose even below room temperature), but some of them are even robust enough to undergo controlled pyrolysis without explosive decomposition at temperatures well above 100 °C. In two cases, the controlled pyrolysis allows the isolation of complex diazaboretidines, which are the apparent dimerization products of endocyclic boryl-iminoboranes