Dipolar and nonpolar altitudinal molecular rotors mounted on an Au(111) surface

We describe the preparation of a compound whose molecules consist of two metal sandwich stands carrying tentacles with affinity to metal surfaces and holding an axle that carries a dipolar or a nonpolar rotator. The dipolar rotor exists as three pairs of enantiomers, rapidly interconverting at room temperature. When mounted on a gold surface, each molecule represents a chiral altitudinal rotor, with the rotator axle parallel to the surface. The surface-mounted rotor molecules are characterized by several spectroscopic and imaging techniques. At any one time, in about one-third of the dipolar rotors the rotator is free to turn and the direction of its dipole can be flipped by the electric field applied by an STM tip, as revealed by differential barrier height imaging. Molecular dynamics calculations suggest that electric field normal to the surface causes members of one pair of enantiomers to rotate unidirectionally.     

Radical addition fragmentation chain transfer (RAFT) polymerization of ferrocenyl (Meth)acrylates

We report on the controlled free radical homopolymerization of 1‐ferrocenylethyl acrylate as well as of three new ferrocene bearing monomers, namely 4‐ferrocenylbutyl acrylate, 2‐ferrocenylamido‐2‐methylpropyl acrylate, and 4‐ferrocenylbutyl methacrylate, by the RAFT technique. For comparison, the latter monomer was polymerized using ATRP, too. The ferrocene containing monomers were found to be less reactive than their analogues free of ferrocene. The reasons for the low polymerizability are not entirely clear. As the addition of free ferrocene to the reaction mixture did not notably affect the polymerizations, sterical hindrance by the bulky ferrocene moiety fixed on the monomers seems to be the most probable explanation. Molar masses found for 1‐ferrocenylethyl acrylate did not exceed 10,000 g mol^?1, while for 4‐ferrocenylbutyl (meth)acrylate molar masses of 15,000 g mol^?1 could be obtained. With PDIs as low as 1.3 in RAFT polymerization of the monomers, good control over the polymerization was achieved. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Enzyme Promiscuity as a Remedy for the Common Problems with Knoevenagel Condensation

A new protocol based on lipase-catalyzed tandem reaction toward α,β-enones/enoesters is presented. For the synthesis of the desired products the tandem process based on enzyme-catalyzed hydrolysis and Knoevenagel reaction starting from enol acetates and aldehyde is developed. The relevant impact of the reaction conditions including organic solvent, enzyme type, and temperature on the course of the reaction was revealed. It was shown that controllable release of the active methylene compound from the corresponding enol carboxylate ensured by enzymatic reaction diminishes significantly the formation of the unwanted co-products. Furthermore, this protocol was extended by including a second tandem chemoenzymatic transformation engaging various aldehyde precursors. After a careful optimization of the reaction conditions, the target products were obtained with yields up to 86 % and with excellent E/Z-selectivity.     

Generating Excess Protons in Microsolvated Acid Clusters under Ambient Conditions: An Issue of Configurational Entropy versus Internal Energy

Acid dissociation, and thus liberation of excess protons in small water droplets, impacts on diverse fields such as interstellar, atmospheric or environmental chemistry. At cryogenic temperatures below 1 K, it is now well established that as few as four water molecules suffice to dissociate the generic strong acid HCl, yet temperature-driven recombination sets in simply upon heating that cluster. Here, the fundamental question is posed of how many more water molecules are required to stabilize a hydrated excess proton at room temperature. Ab initio path integral simulations disclose that not five, but six water molecules are needed at 300 K to allow for HCl dissociation independently from nuclear quantum effects. In order to provide the molecular underpinnings of these observations, the classical and quantum free energy profiles were decomposed along the dissociation coordinate in terms of the corresponding internal energy and entropy profiles. What decides in the end about acid dissociation, and thus ion pair formation, in a specific microsolvated water cluster at room temperature is found to be a fierce competition between classical configurational entropy and internal energy, where the former stabilizes the undissociated state whereas the latter favors dissociation. It is expected that these are generic findings with broad implications on acid–base chemistry depending on temperature in small water assemblies.     

Stereoselective Cascade Cyclizations with Samarium Diiodide to Tetracyclic Indolines: Precursors of Fluorostrychnines and Brucine

A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible.     

Semi-active stabilisation of a pipe conveying fluid using eddy-current dampers: state-feedback control design,experimental validation

An application of electromagnetic devices of the motional type (i.e. eddy-current dampers) to improve the dynamic stability of a cantilever pipe discharging fluid is proposed. When the flow velocity reaches a critical value, this system loses stability through the flutter. A contactless damping device is used. This actuator is made of a conducting plate attached to the pipe that moves together with it within the perpendicular magnetic field that is generated by the controlled electromagnets. During the motion the eddy currents in the plate and a resultant drag force of a viscous character are generated. First, an optimal control problem that aims to stabilise the system with the optimal rate of decrease of the system’s energy is posed and solved. Then a state-feedback parametrization of the obtained optimal control, which can be used in a closed-loop scheme is proposed. The effectiveness of the designed optimal controller is validated by making a comparison with the corresponding passive solutions on the specially designed and constructed experimental test stand of a pipe conveying air.