Photocatalytic Reduction of Nicotinamide Co-factor by Perylene Sensitized RhIII Complexes**

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene-based light-harvesting moiety and a catalytic rhodium center ( Rh^IIIphenPer ). The excited-state dynamics were investigated by means of steady-state and time-resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of Rh^IIIphenPer yields the formation of a charge-separated intermediate, namely Rh^IIphenPer ⋅ ⁺ , that results in a catalytically active species in the presence of protons.     

Total Synthesis of Resveratrone and iso-Resveratrone

The first total synthesis of resveratrone and iso-resveratrone based on an epoxide olefination approach is described. The pivotal reaction proceeds by insertion of the lithiated epoxide into a boronic ester and subsequent syn-elimination. Resveratrone has been described to have remarkable photophysical properties, including two-photon absorption. Therefore, an azide derivative has been prepared to allow for use as a biological label.     

The Effect of the Side Chain on Gelation Properties of Bile Acid Alkyl Amides

Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all six compounds were studied for 36 solvents with varying polarities. Gelation was observed mainly in aromatic solvents, which is characteristic for bile-acid-based low molecular weight gelators. Out of 108 bile acid-solvent combinations, a total of 44 gel systems were formed, 28 of which from lithocholic acid derivatives, only two from deoxycholic acid derivatives, and 14 from cholic acid derivatives. The majority of the gel systems were formed from bile acids with hexyl side chains, contrary to the cyclohexyl group, which seems to be a poor gelation moiety. These results indicate that the spatial demand of the side chain is the key feature for the gelation properties of the bile acid amides.     

Microwave photonic crystal on the slot transmission line with a ferroelectric film

A microwave electrically tunable photonic crystal based on a periodically width-modulated slot transmission line with a ferroelectric film is investigated for the first time. The dispersion and transmission characteristics of electromagnetic waves propagating in such a structure are calculated. The electric control over photonic crystal characteristics is simulated.     

Optical aperture area determination for accurate illuminance and luminous efficacy measurements of LED lamps

The measurement uncertainty of illuminance and, consequently, luminous flux and luminous efficacy of LED lamps can be reduced with a recently introduced method based on the predictable quantum efficient detector (PQED). One of the most critical factors affecting the measurement uncertainty with the PQED method is the determination of the aperture area. This paper describes an upgrade to an optical method for direct determination of aperture area where superposition of equally spaced Gaussian laser beams is used to form a uniform irradiance distribution. In practice, this is accomplished by scanning the aperture in front of an intensity-stabilized laser beam. In the upgraded method, the aperture is attached to the PQED and the whole package is transversely scanned relative to the laser beam. This has the benefit of having identical geometry in the laser scanning of the aperture area and in the actual photometric measurement. Further, the aperture and detector assembly does not have to be dismantled for the aperture calibration. However, due to small acceptance angle of the PQED, differences between the diffraction effects of an overfilling plane wave and of a combination of Gaussian laser beams at the circular aperture need to be taken into account. A numerical calculation method for studying these effects is discussed in this paper. The calculation utilizes the Rayleigh–Sommerfeld diffraction integral, which is applied to the geometry of the PQED and the aperture. Calculation results for various aperture diameters and two different aperture-to-detector distances are presented.     

Reaction kinetics and solubility in water‐organic binary solutions are governed by similar solvation equilibria

The solvation effects observed in water‐organic solutions were studied by combining data for reaction kinetics and dissolution equilibria by means of a linear free‐energy (similarity) analysis. Kinetic data for the pH‐independent hydrolysis of (4‐methoxyphenyl)‐2,2‐dichloroacetate measured in this work and solubility data for naphthalene, and other substrates of low polarity, in aqueous binary mixtures of methanol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), and 1,4‐dioxane were used. Linear similarity relationships were discovered for these data over the full range of solvent compositions studied. To gain insight into the similarities observed between these different phenomena, molecular dynamics simulations were carried out for naphthalene and an ester in water–acetonitrile solutions. The results revealed considerable preferential solvation of these substrates by the co‐solvent. Linear relationships between the experimental data and the mole fractions of acetonitrile in the solvation shells of substrates were found. Surprisingly, a linear relationship was found between the mole fractions of acetonitrile in the solvation shells of the ester and naphthalene. This linearity indicated that a similar solvation mechanism governs even such different phenomena as dissolution and reaction kinetics. The relationships between the experimental data and the results of the molecular dynamics calculations found in this work explained the solvent effect observed in water‐organic solutions on the molecular level. Copyright © 2015 John Wiley & Sons, Ltd.     

Taming instabilities in power grid networks by decentralized control

Renewables will soon dominate energy production in our electric power system. And yet, how to integrate renewable energy into the grid and the market is still a subject of major debate. Decentral Smart Grid Control (DSGC) was recently proposed as a robust and decentralized approach to balance supply and demand and to guarantee a grid operation that is both economically and dynamically feasible. Here, we analyze the impact of network topology by assessing the stability of essential network motifs using both linear stability analysis and basin volume for delay systems. Our results indicate that if frequency measurements are averaged over sufficiently large time intervals, DSGC enhances the stability of extended power grid systems. We further investigate whether DSGC supports centralized and/or decentralized power production and find it to be applicable to both. However, our results on cycle-like systems suggest that DSGC favors systems with decentralized production. Here, lower line capacities and lower averaging times are required compared to those with centralized production.     

Synchronization patterns and chimera states in complex networks: Interplay of topology and dynamics

We review chimera patterns, which consist of coexisting spatial domains of coherent (synchronized) and incoherent (desynchronized) dynamics in networks of identical oscillators. We focus on chimera states involving amplitude as well as phase dynamics, complex topologies like small-world or hierarchical (fractal), noise, and delay. We show that a plethora of novel chimera patterns arise if one goes beyond the Kuramoto phase oscillator model. For the FitzHugh-Nagumo system, the Van der Pol oscillator, and the Stuart-Landau oscillator with symmetry-breaking coupling various multi-chimera patterns including amplitude chimeras and chimera death occur. To test the robustness of chimera patterns with respect to changes in the structure of the network, regular rings with coupling range R, small-world, and fractal topologies are studied. We also address the robustness of amplitude chimera states in the presence of noise. If delay is added, the lifetime of transient chimeras can be drastically increased.     

Tuning the Lewis acid phenol $$\varvec{}$$-prenylation as a molecular diversity tool

A diversity-oriented approach for the synthesis of various structurally different prenylated alcohols from readily accessible and common precursors was developed. With varying approaches, this article describes some successful examples of a Friedel–Crafts alkylation using methoxyphenols and different prenyl alcohols (geraniol and (E,E)-farnesol). We demonstrated that just by varying the stoichiometry of the Lewis acid used, the course of the reaction can be shifted to produce the alkylated or the cyclized product. Eighteen unique products were obtained with good isolated yields by direct alkylation with or without a consecutive \(\pi \)-cationic cyclization.     

Effective fields in laser-driven electron recollision and charge localization

We propose a model to describe correlated two-electron dynamics in strong laser fields during laser-induced recollision between an electron and its parent ion. We derive an effective interaction potential which describes the effect of the laser-driven electron collision with an ion while retaining the correlation between the colliding and the bound electron. Using dissociative ionization of molecular hydrogen as an example, we analyze the dynamics of correlation-driven electron localization in a dissociating hydrogen molecular ion.