Aus kleinen Dingen werden große: 14‐Helicale N‐Acetyl‐β3‐peptide bilden in Lösung spontan in einer einzigartigen Kopf‐Schwanz‐Verknüpfung Fasern. Die Fasergröße lässt sich vom Nano‐ bis zum Makrobereich einstellen. Die inhärente Flexibilität im Design und die einfache Synthese bieten neue leistungsfähige Möglichkeiten für die Entwicklung von Bio‐ und Nanomaterialien durch supramolekulare Selbstorganisation.

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In this study, the performance of 17 different density functional theory functionals was compared for the calculation of the bond dissociation energy (BDE) values of X−H (X=C, N, O, S) bonds of aromatic compounds. The effect of the size of the basis set (expansions of 6-31(G)) was also assessed for the initial geometry and zero-point energy calculations, followed by the single-point BDE calculations with different model chemistries with the 6-311 + (3df,2p) basis set. It was found that the size of the basis set for geometry optimization has a much smaller effect on the accuracy of BDE than the choice of functional for the following single-point calculations. The M06-2X, M05-2X and M08−HX functionals yielded highly accurate BDE values compared to experimental data (with the average mean unsigned error MUE = 1.2–1.5 kcal mol −1 ), performing better than any of the other functionals. The results suggest that geometry optimization may be performed with B3LYP functional and a small basis set, whereas the M06-2X, M05-2X and M08-HX density functionals with a suitably large basis set offer the best method for calculating BDEs of ArX−H (X=C, N, O, S) bonds.

Optical field distribution in micro-nano geometries of miniaturized optical devices is often significantly different from that in identical but macroscopic geometries. Plasmon effects and near-field diffraction can enhance the local field intensity, leading to enhanced cross section for light absorption and scattering, which can be utilized in substrate-enhanced spectroscopies for the detection of trace amounts of adsorbed chemicals. A specific problem is an ingenious but only empirically described way to enhance signal intensity in Raman spectroscopy by the use of a substrate patterned with gold coated micron size pyramidal pits. While Raman enhancement on nanostructured substrates is generally attributed to surface plasmons, here the micron size, and thus the sub-wavelength to near-wavelength dimensions suggest that resonant enhancement emanating from optical near-field diffraction might also play a role. To answer this question, light diffraction in a projection of the pyramidal pit: a V-groove, was modelled with a modified Neerhoff-Mur formalism suitable to calculate electromagnetic field distribution in sub-wavelength structures. Under the boundary conditions a perfect conductor screen was assumed, which excludes plasmon effects. The calculations show that interference in the cavity causes a modest resonant increase in local intensity and that near-field diffraction strongly influences the field distribution, which is explained with the electrodynamic edge effect. The magnitude of the resonant electric field on its own cannot account for the experimentally observed Raman enhancement. However, a resonant enhancement of a similar magnitude is expected for the emitted Stokes frequencies. In this case the geometry implements the conditions for the classical electromagnetic Raman enhancement, ~E(4), in a good agreement with experimental results.