Reaktionen auf der Spur

A new technique, desorption electrospray ionization coupled to mass spectrometry (DESI‐MS), has been used as a tool for reaction analysis. Charged droplets of a reagent are sprayed onto the catalyst, which has previously been deposited on a surface in front of a mass analyzer. The reaction starts as the droplets impact the catalyst on the surface and continues inside secondary microdroplets that are desorbed from the surface. These are directed toward the mass spec inlet. Using this technique, the very first milliseconds of a reaction can be observed. The first example describes the discovery of an extremely short‐lived intermediate in a C‐H amination reaction cycle. Another example describes how DESI‐MS has been used to identify catalyst arrest mechanisms in ruthenium catalyzed C‐H hydroxylation.     

Photochirogenesis: photochemical models on the absolute asymmetric formation of amino acids in interstellar space

Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.     

Controlling ghost traps in holographic optical tweezers

Computer-generated holograms displayed by phase-modulating spatial light modulators have become a well-established tool for beam shaping purposes in holographic optical tweezers. Still, the generation of light intensity patterns with high spatial symmetry and simultaneously without interfering ghost traps is a challenge. We have implemented an iterative Fourier transform algorithm that is capable of controlling these ghost traps and demonstrate the benefit of this approach in the experiment.     

Domain-shape-based modulation of Čerenkov second-harmonic generation in multidomain strontium barium niobate

We study experimentally and numerically the second-harmonic ?erenkov emission with two different characteristic azimuthal intensity distributions in strontium barium niobate with a random structure of χ2 nonlinearity. We monitor in situ the ?erenkov emission during domain switching and show that a change of domain size and shape results in a fourfold azimuthal modulation of the ?erenkov cone.     

Bubble dynamics: Long-time behavior and interaction in viscous liquids

A mathematical two-phase model is used to numerically investigate physical and rheological effects on small, individual bubbles in high-viscosity liquids under pressure impact. It is found out that bubbles remain stable over time at high viscosity and surface tension. The steady case is considered and connected to the stability behavior of the bubble. An upper bound for the bubble radius is derived and the new equilibrium state of the bubble can be predicted by means of stability theorems of differential equations. Finally, the interaction of a limited number of well separated bubbles in an Hele-Shaw flow is mathematically analyzed to visualize and physically interpret their trajectories. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)