Self-induced oscillations in an optomechanical system driven by bolometric backaction

We have explored the nonlinear dynamics of an optomechanical system consisting of an illuminated Fabry-Perot cavity, one of whose end mirrors is attached to a vibrating cantilever. The backaction induced by the bolometric light force produces negative damping such that the system enters a regime of nonlinear oscillations. We study the ensuing attractor diagram describing the nonlinear dynamics. A theory is presented that yields quantitative agreement with experimental results. This includes the observation of a regime where two mechanical modes of the cantilever are excited simultaneously.     

Photostability of Cosmetic UV Filters on Mammalian Skin Under UV Exposure

Previous studies showed that the common UV filter substances benzophenone‐3 (BP–3), butyl methoxydibenzoylmethane (BM–DBM), octocrylene (OCR), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS) and ethylhexyl triazone (EHT) were able to react with amino side chains of different proteins in vitro. To transfer the results to mammalian skin conditions, sunscreen products were applied on both prepared fresh porcine skin and glass plates, followed by UV irradiation and the determination of depletion of the respective UV filters. Significantly lower recoveries of the UV filters extracted from skin samples than from glass plates indicated the additional reaction of the UV filters with skin constituents, when proteins will be the most important reactants. Among the products tested, BP‐3 showed the greatest differences in recoveries between glass and skin samples of about 13% and 24% after 2 and 4 h of irradiation, respectively, followed by EHS > BM‐DBM > OCR > EHMC > EHT. The obtained results raise the question, whether the common in vitro evaluations of sunscreens, using inert substrate materials like roughened quartz or polymethyl methacrylate (PMMA) plates are really suitable to fully replace in vivo methods, as they cannot include skin‐typical reactions.     

Catechol Thioesters: Ligands for Hierarchically Formed Lithium-Bridged Titanium(IV) Helicates and Helicate-Based Switches

The thioester moiety is introduced as a lithium binding unit for the hierarchical formation of titanium(IV) catecholate-based lithium-bridged helicates. In solution, the coordination compounds show a monomer–dimer equilibrium which —in comparison to the oxo esters— is significantly shifted towards the monomers. In addition, the influence of the thioester side chain on the dimerization behavior is investigated and an expansible/compressible molecular switch is synthesized. In the latter case expansion and compression are performed reversibly in methanol, whereas in DMSO spontaneous expansion occurs.     

Rapid spectroscopic velocity quantification using periodically oscillating gradients

In this work two spectroscopic methods are described which allow rapid flow velocity quantification in the presence of a parabolic velocity distribution. This method requires only a single excitation and is based on flow encoding by periodically oscillating gradients. In the shown spin echo variant additional refocusing pulses correct for field inhomogeneities. A theoretical model is introduced, which describes the course of the derived spectra even in high flow region, where a significant part of the encoded spins leaves the sensitive area of the coil during data acquisition (outflow-effect). It was demonstrated that both methods can quantify flow velocities within the velocity range of 1mm/s up to 36 cm/s in the presence of a parabolic flow velocity distribution. The maximum velocity of the parabolic distribution is indicated in this method by a peak in the acquired spectrum from which the velocity could be quantified. Flow velocity quantification by periodically oscillating gradients seems a reasonable and fast alternative to established imaging techniques.     

Determining the enantioselectivity of chiral catalysts by mass spectrometric screening of their racemic forms

The enantioselectivity of a chiral catalyst can be determined from its racemic form by mass spectrometric screening of a nonequal mixture of two mass-labeled quasienantiomeric substrates. The presented method opens up new possibilities for evaluating catalyst structures that are not readily available in enantiomerically pure form.     

An unexpected and easy way of freezing the configuration of a triaryl phosphane oxide

Configurationally stable triaryl phosphane oxides are important for reactions with transfer of chiral information. Apart from introducing bulky substituents to suppress fast inversion of helicity at room temperature, the use of a second chiral element which induces chirality in the triaryl phosphane oxide, so that it adopts only one configuration, is suitable. With regard to chirality transfer, C(2)-symmetric imidazole cyclopeptides were tested for obtaining a configurationally stable phosphane oxide. Density functional calculations showed almost equal energies of the three possible triaryl phosphane oxides (MMM)-1, (PPP)-1, and (MP)-1. Surprisingly, after synthesis only the MMM conformer is present in solution, and its configurational stability was proved by variable-temperature and 2D NMR experiments as well as CD measurements. In view of the results of the DFT calculations, formation of stable (MMM)-1 cannot be explained thermodynamically but by kinetic reaction control. This concept of freezing the conformation of a triaryl phosphane oxide can in future be used to easily prepare configurationally stable stereoisomeric propellerlike compounds.