An amphibious vibration-driven microrobot with a piezoelectric actuator

This article concerns microrobots for solid and liquid environments. A short overview of microrobotics, suitable actuators and energy systems is given. The principles of terrestrial and aquatic locomotion are discussed and illustrated with examples from the literature on robotics. The state of the art with a focus on piezo microrobots for solid and liquid environments is presented. Furthermore, we report an amphibious prototype, which can move on flat solid ground and on the free surface of water. The design, characteristic parameters and experiments on locomotion are described. The robot is characterized by a light and simple design and can perform twodimensional locomotion in different environments with a speed up to 30 mm/s. An analytical model to predict the maximum carrying capacity of the robot on water is solved numerically.     

Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.     

Proto‐Urea‐RNA (Wöhler RNA) Containing Unusually Stable Urea Nucleosides

The RNA world hypothesis assumes that life on Earth began with nucleotides that formed information‐carrying RNA oligomers able to self‐replicate. Prebiotic reactions leading to the contemporary nucleosides are now known, but their execution often requires specific starting materials and lengthy reaction sequences. It was therefore proposed that the RNA world was likely proceeded by a proto‐RNA world constructed from molecules that were likely present on the early Earth in greater abundance. Herein, we show that the prebiotic starting molecules bis‐urea (biuret) and tris‐urea (triuret) are able to directly react with ribose. The urea‐ribosides are remarkably stable because they are held together by a network of intramolecular, bifurcated hydrogen bonds. This even allowed the synthesis of phosphoramidite building blocks and incorporation of the units into RNA. Investigations of the nucleotides’ base‐pairing potential showed that triuret:G RNA base pairs closely resemble U:G wobble base pairs. Based on the probable abundance of urea on the early Earth, we postulate that urea‐containing RNA bases are good candidates for a proto‐RNA world.     

Novel Aspects in the Synthesis of Carbenoids Containing P/C-pπ-Bonds

Abstract

The synthesis and x-ray structure analysis of a novel type of carbenoids, aryl-P(=E)=C(Cl)Li(thf)₃ (E=N-aryl, C(SiMe₃)₂), as well as the first example of a 1,3-diphosphetane-2,4-diyl, (aryl-PCCl)₂, is reported and on the basis of quantum chemical calculations its bonding situation is discussed. Furthermore, selected examples for the varying reaction behavior of both types of compounds are presented.