Synthesis of Fluorinated Graphene Oxide and its Amphiphobic Properties

The richly functionalized basal plane bonded to polar organic moieties makes graphene oxide (GO) innately hydrophilic. Here, a methodology to synthesize fluorinated graphene oxide by oxidizing the basal plane of fluorinated graphite, allowing for tunable hydrophobicity of GO, is reported. Fluorine exists as tertiary alkyl fluorides covalently bonded to graphitic carbons, and using magic‐angle spinning (MAS) ¹³C NMR as a primary tool chemical structures for the two types of synthesized fluorinated graphene oxides (FGOs) with significantly different fluorine contents are proposed. The low surface energy of the C–F bond drastically affects GO's wetting behavior, leading to amphiphobicity in its highly fluorinated form. Ease of solution processing enables the fabrication of inks that are spray‐painted on various porous/non‐porous substrates. These coatings maintain amphiphobicity for solvents with surface tensions down to 59 dyn/cm, thus bypassing existing lithographic means to create similar surfaces. The approach towards fluorinating GO and fabricating graphene‐based surfaces with tunable wettability opens the path towards unique, accessible, carbon‐based amphiphobic coatings.     

A novel monochromator for experiments with ultrashort X‐ray pulses

Aiming at advancing storage‐ring‐based ultrafast X‐ray science, over the past few years many upgrades have been undertaken to continue improving beamline performance and photon flux at the Femtoslicing facility at BESSY II. In this article the particular design upgrade of one of the key optical components, the zone‐plate monochromator (ZPM) beamline, is reported. The beamline is devoted to optical pump/soft X‐ray probe applications with 100 fs (FWHM) X‐ray pulses in the soft X‐ray range at variable polarization. A novel approach consisting of an array of nine off‐axis reflection zone plates is used for a gapless coverage of the spectral range between 410 and 1333 eV at a designed resolution of E/ΔE = 500 and a pulse elongation of only 30 fs. With the upgrade of the ZPM the following was achieved: a smaller focus, an improved spectral resolution and bandwidth as well as excellent long‐term stability. The beamline will enable a new class of ultrafast applications with variable optical excitation wavelength and variable polarization.     

Quantum field theory of phase transitions in Fermi systems

The theory of fermion phase transitions is reviewed from a unified field theoretic standpoint, based on the diagrammatic perturbation expansion of a generalized matrix propagator. Transitions from a normal to a condensed phase are characterized by the spontaneous appearance of long-range order and (in the presence of a suitable infinitesimal external field) broken symmetry. This is illustrated by the ferromagnetic, solid, superconducting and spindensity wave ground states. The phenomenon is explained qualitatively as caused by the creation of a long-range internal field, F, due to the interactions between particles. This field establishes long-range order in the system, and is in turn itself established by the long-range order, in a self-consistent fashion. The mechanism here is expressed quantitatively in terms of a self-consistent Dyson equation relating a generalized matrix propagator, G, to a proper self-energy matrix, Σ. The off-diagonal elements of G describe ‘anomalous’ propagation processes which are characteristic for the condensed phase, and they yield directly the long-range order parameters. The Σ-matrix is just the potential of the internal field. The method is illustrated by applying it to the ferromagnetic phase of a system with δ-function interaction between particles. Finally, the technique is used to derive the vertex part equation for the transition point.     

13C-Leucin-Atemtest zur Beurteilung der anabolen Verwertung von diätetischen Aminosäurengemischen bei Phenylketonurie

It is essential to establish whether and how environmental factors affect the reliability of [¹³C]methacetin breath test (¹³C-MBT). In 12 healthy volunteers (smokers), a standard ¹³C-MBT with 75 mg [¹³C]methacetin was performed twice in random order: on a control day without smoking and on another day with smoking two cigarettes antecedently. A considerable flattening of the curve of the momentary ¹³C recovery within the expiratory air was observed when the ¹³C-MBT was performed after smoking. The maximum of the momentary ¹³C recovery, D _max, decreased from 37.20±2.58 to 25.39±2.29% dose/h (p=0.00052). Moreover, the time to reach D _max was prolonged after cigarette smoking (26.5±3.1 vs. 16.5±1.9 min, p=0.0199). The curve of the cumulative ¹³C recovery on the cigarette smoking day appeared to be shifted downwards, and statistically significant differences relative to the control situation were found between the 24th and 75th minute following [¹³C]methacetin administration. Smoking cigarettes immediately prior to the ¹³C-MBT diminishes the ability of the liver to handle methacetin, and hence a possibility of such an interaction should be excluded in order to interpret the results of the test correctly.     

Isotope Geochemical Studies on Carbonates of Quaternary Glacio-Lacustrine Lake Sediments as indicators of Paleoenvironment

Selected silty “summer” and argillaceous “winter” layers of profiles of the rhythmically bedded glacio-lacustrine ice-marginal lake sediment of the Dehlitz-Leipzig varved clay (Leipziger Tieflandsbucht, Central Germany) have been examined for isotope composition (¹⁸O/¹⁶O, ¹³C/¹²C) of carbonate and organic fraction. In addition, mineralogical and grain size compositions were determined. The results show 1) a change in source of carbonate sediment (provenance) through time; 2) the oxygen isotope ratios differed between the “summer” and “winter” layers of varves couplets due to different rates of sedimentation; 3) anoxic events occurred in the lake; 4) carbon isotope ratios suggest organics in lake sediments which were derived from land and the primary productivity was low in the lake itself. In the study of cold-climatic lake sediments, isotope investigations can efficiently be used as additional paleosedimentological and facies indicators.     

15N-Traceruntersuchungen zum Mechanismus der N2O-Bildung in Böden

Nitrous oxide is a potential environmental hazard responsible for the green house effect and the destruction of the ozone layer in the lower stratosphere. Biological denitrification under anaerobic conditions in soils results in the formation of both N₂O and N₂, whereby highly nitrogen-fertilized agricultural soils contribute to a considerable extent of the N₂O emission. Latest results in the literature indicate that nitrous oxide can also be formed as a byproduct of the microbial nitrification. This is of importance for soils in central Germany because of the non-existence of typical denitrification conditions in a semiaride climate.

This study was conducted to measure the path of N₂O formation in Haplic Phaeozen: using [¹⁵N] ammonium and [¹⁵N] nitrat and a GC-MS aided incubation system. The kinetic isotope method was used to evaluate the experimental data. The results are:

- Under anaerobic conditions (～ 90% of the water holding capacity = WHC) N₂O originates mainly from the nitrate pool by denitrification.

- As expected, the N₂O formation is low under aerobic conditions (～ 80% WHC) but the gas originates directly from the ammonium and not from the nitrate pool, probably as a byproduct of the nitrification process.     

High-resolution,near-infrared CW-CRDS,and ab initio investigations of N2O–HDO

We have investigated the N₂O–HDO molecular complex using ab initio calculations at the CCSD(T)-F12a/aug-cc-pVTZ level of theory and using cavity ring-down spectroscopy to probe an HDO/N₂O/Ar supersonic jet around 1.58 μm. A single a-type vibrational band was observed, 13 cm^?1 redshifted compared to the OH+OD excited band in HDO, and 173 vibration-rotation lines were assigned (T_rot ≈ 20 K). A weighted fit of existing microwave and present near infrared (NIR) data was achieved using a standard Watson's Hamiltonian (σ = 1.26), producing ground and excited states rotational constants. The comparison of the former with those calculated ab initio suggests a planar geometry in which the OD rather than the OH bond in water is almost parallel to NNO. The equilibrium geometry and dissociation energy (D_e = –11.7 kJ/mol) of the water–nitrous oxide complex were calculated. The calculations further demonstrate and allow characterising another minimum, 404 cm^?1 (ΔE₀) higher in energy. Harmonic vibrational frequencies and dissociation energies, D₀, were calculated for various conformers and isotopic forms of the complex, in both minima. The absence of N₂O–D₂O from dedicated NIR experiments is reported and discussed.     

Research Note

Formulas are derived for consistent evaluation of permutationally totally symmetric and determinantally antisymmetric powers of generalized combinations in which irreducible representations may occur with either positive or negative weights.