Aetherische Oele

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Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

Ca3N2 and Mg3N2: unpredicted high-pressure behavior of binary nitrides

High-pressure synthesis allows both fundamental and materials science research to gain unprecedented insight into the inner nature of materials properties at extreme environment conditions. Here, we report on the high-pressure synthesis and characterization of γ-Ca(3)N(2) and the high-pressure behavior of Mg(3)N(2). Investigation of M(3)N(2) (M = Ca, Mg) at high-pressure has been quite challenging due to the high reactivity of these compounds. Ex situ experiments have been performed using a multianvil press at pressures from 8 to 18 GPa (1000-1200 °C). Additional in situ experiments from 0 to 6 GPa (at RT) at the multianvil press MAX 80 (HASYLAB, Beamline F.2.1, Hamburg) have been carried out. The new cubic high-pressure phase γ-Ca(3)N(2) with anti-Th(3)P(4) defect structure exhibits a significant increase in coordination numbers compared to α-Ca(3)N(2). Contrary, Mg(3)N(2) shows decomposition starting at surprisingly low pressures, thereby acting as a precursor for Mg nanoparticle formation with bcc structure. Soft X-ray spectroscopy in conjunction with first principles DFT calculations have been used to explore the electronic structure and show that γ-Ca(3)N(2) is a semiconductor with inherent nitrogen vacancies.     

Stereoselective synthesis of deuterated β-cyclohexenylserine, a biosynthetic intermediate of the salinosporamides

A straightforward, highly stereoselective protocol toward the synthesis of deuterium-labeled (2R,3S,4S)-β-cyclohexenylserine has been developed. Key steps are a Nozaki-Hiyama-Kishi reaction generating the stereogenic centers and a ring-closing metathesis for the construction of the cyclohexenyl ring system. The labeled amino acid was further activated as an SNAc-ester for feeding experiments.     

Structural characterization of artificial self-assembling porphyrins that mimic the natural chlorosomal bacteriochlorophylls c, d, and e

We report two crystal structures of a synthetic porphyrin molecule which was programmed for self-assembly. The same groups which ensure that bacteriochlorophylls c, d, and e can self-assemble into the chlorosomal nanorods, the photosynthetic antenna system of some green bacteria, have been engineered into desired positions of the tetrapyrrolic macrocycle. In the case of the 5,15-meso-substituted anchoring groups, depending upon the concentration, by using the same crystallization solvents, either a tetragonal or a layered structure of porphyrin stacks were encountered. Surprisingly, pi-pi interactions combined with extensive dispersive interactions, which also encompass cyclohexane, one of the crystallization solvents, win over putative hydrogen bonding. We are aware that our compounds differ considerably from the natural bacteriochlorophylls, but based upon our findings, we now question the hydrogen-bonding network, previously proposed to organize stacks of bacteriochlorophylls. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) on various isomeric compounds support our challenge of current models for the chlorosomal antenna as these show structures, astonishingly similar to those of chlorosomes.     

Sound segregation based on temporal envelope structure and binaural cues

The ability to segregate two spectrally and temporally overlapping signals based on differences in temporal envelope structure and binaural cues was investigated. Signals were a harmonic tone complex (HTC) with 20 Hz fundamental frequency and a bandpass noise (BPN). Both signals had interaural differences of the same absolute value, but with opposite signs to establish lateralization to different sides of the medial plane, such that their combination yielded two different spatial configurations. As an indication for segregation ability, threshold interaural time and level differences were measured for discrimination between these spatial configurations. Discrimination based on interaural level differences was good, although absolute thresholds depended on signal bandwidth and center frequency. Discrimination based on interaural time differences required the signals' temporal envelope structures to be sufficiently different. Long-term interaural cross-correlation patterns or long-term averaged patterns after equalization-cancellation of the combined signals did not provide information for the discrimination. The binaural system must, therefore, have been capable of processing changes in interaural time differences within the period of the harmonic tone complex, suggesting that monaural information from the temporal envelopes influences the use of binaural information in the perceptual organization of signal components.