Triphilic Ionic‐Liquid Mixtures: Fluorinated and Non‐fluorinated Aprotic Ionic‐Liquid Mixtures

We present here the possibility of forming triphilic mixtures from alkyl‐ and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self‐associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long‐range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment.     

Immobilized β-cyclodextrin on surface-modified carbon-coated cobalt nanomagnets: reversible organic contaminant adsorption and enrichment from water

Surface-modified magnetic nanoparticles can be used in extraction processes as they readily disperse in common solvents and combine high saturation magnetization with excellent accessibility. Reversible and recyclable adsorption and desorption through solvent changes and magnetic separation provide technically attractive alternatives to classical solvent extraction. Thin polymer layered carbon-coated cobalt nanoparticles were tagged with β-cyclodextrin. The resulting material reversibly adsorbed organic contaminants in water within minutes. Isolation of the immobilized inclusion complex was easily carried out within seconds by magnetic separation due to the strong magnetization of the nanomagnets (metal core instead of hitherto used iron oxide). The trapped molecules were fully and rapidly recovered by filling the cyclodextrin cavity with a microbiologically well accepted substitute, e.g., benzyl alcohol. Phenolphthalein was used as a model compound for organic contaminants such as polychlorinated dibenzodioxins (PCDDs) or bisphenol A (BPA). Fast regeneration of nanomagnets (compared to similar cyclodextrin-based systems) under mild conditions resulted in 16 repetitive cycles (adsorption/desorption) at full efficiency. The high removal and regeneration efficiency was examined by UV-vis measurements at chemical equilibrium conditions and under rapid cycling (5 min). Experiments at ultralow concentrations (160 ppb) underline the high potential of cyclodextrin modified nanomagnets as a fast, recyclable extraction method for organic contaminants in large water streams or as an enrichment tool for analytics.     

Synthesis, electronic, and electro-optical properties of emissive solvatochromic phenothiazinyl merocyanine dyes

Phenothiazinyl merocyanine dyes with variable substitution patterns on the peripheral benzene ring were synthesized in good yields by Knoevenagel condensation of the corresponding phenothiazinyl aldehydes and N-methylrhodanine or indan-1,3-dione. The electronic properties were investigated by cyclic voltammetry, absorption, electro-optical absorption, and emission spectroscopy. All these merocyanines reveal reversible redox behavior that stems from the phenothiazinyl-centered oxidation to give stable radical cations. The redox potentials strongly correlate with Hammett σ(p) parameters. All merocyanines reveal large Stokes shifts. They also display a pronounced emissive solvatochromism, which is caused by large dipole moment changes upon excitation from the ground to the excited state. These findings are supported by solvatochromism studies and time-dependent DFT computations.     

Electronic coupling and scaling effects during dielectric barrier electrospray ionization

The mechanism of the previously published technique of dielectric barrier electrospray ionization (DB-ESI) was investigated in more detail. Two independent current signals occurring during the DB-ESI could be explained and allocated to sub-processes. The modulated shape of the HV signal, the applied frequency as well as the inner diameter of the emitter capillary have a big impact on the spray. Furthermore, there exists a cut-off frequency which depends on the electronic properties of the DB-ESI interface. Comparable mass spectra for lysine employing both conventional ESI and DB-ESI show a good analytical potential of the new technique.     

The Edge Correlation of Random Forests

The conjecture was made by Kahn that a spanning forest F chosen uniformly at random from all forests of any finite graph G has the edge-negative association property. If true, the conjecture would mean that given any two edges ε₁ and ε₂ in G, the inequality \mathbbP(e₁ ? F, e₂ ? F) ￡ \mathbbP(e₁ ? F)\mathbbP(e₂ ? F){{\mathbb{P}(\varepsilon_{1} \in \mathbf{F}, \varepsilon_{2} \in \mathbf{F}) \leq \mathbb{P}(\varepsilon_{1} \in \mathbf{F})\mathbb{P}(\varepsilon_{2} \in \mathbf{F})}} would hold. We use enumerative methods to show that this conjecture is true for n large enough when G is a complete graph on n vertices. We derive explicit related results for random trees.