Fluoride has been overlooked as a target in the development of synthetic anion transporters despite natural fluoride transport channels being recently discovered. In this paper we report the direct measurement of fluoride transport across lipid bilayers facilitated by a series of strapped calix[4]pyrroles and show that these compounds facilitate transport via an electrogenic mechanism (determined using valinomycin and monensin coupled transport assays and an additional osmotic response assay). An HPTS transport assay was used to quantify this electrogenic process and assess the interference of naturally occurring fatty acids with the transport process and Cl over H/OH transport selectivity.
In this study, the anion-binding bis(cyclopeptide) 2 is introduced, which dissolves freely in water, affording up to 10 mM concentrations, thanks to triethylene glycol-derived substituents in the cyclopeptide subunits and the linker connecting them. Binding studies provided evidence that the anion affinity previously demonstrated for less-soluble analogs of this compound is retained under highly competitive aqueous conditions. The highest affinity in water was observed for iodide, closely followed by sulfate anions, whereas binding of soft and weakly coordinating anions could not be observed. The anion selectivity of 2 thus differs from that of other recently described receptors, which also do not require electrostatic or coordinative interactions for anion binding in water but typically fail to bind strongly coordinating sulfate anions. The ability of 2 to overcome sulfate hydration is attributed to the special mode of binding, combining direct N–H···A – interactions with the release of water molecules from the receptor cavity. The characterization of the anion binding of 2 and a related bis(cyclopeptide) in a variety of different solvents and aqueous solvent mixtures furthermore allowed the correlation of the binding properties with solvent parameters. These analyses provided qualitative and even quantitative insights into the solvent properties and solvation phenomena that mainly affect anion complexation.
The influence of electron heating compared to ion heating on plasma performance has been analysed in order to make valid projections towards future devices. The capabilities of the newly upgraded electron cyclotron resonance heating system at ASDEX Upgrade make this analysis feasible by replacing neutral beam injection. Dominantly electron heated plasmas are analysed and compared to dominantly ion heated plasmas. It is investigated if they behave systematically different or if the change of heated species is fully compensated by heat exchange from electrons to ions. Studies of plasmas at high collisionalities are presented in Sommer et al (2012 Nucl. Fusion 52 114018). Here, these former investigations are extended towards lower collisionalities. The global plasma parameters show a slight reduction with increasing electron heating arising from a significant decrease of the ion temperature, whereas the electron temperature profile is unchanged. The density profile shows a strong peaking which remains unchanged when modifying the heating mix. The power balance analysis shows an important impact of the heat exchange between electrons and ions. The electron and ion temperatures and the plasma density are modelled with the transport model TGLF. The experimental observations are reproduced verifying the applied code. Linear gyrokinetic calculations with GS2 found the ion temperature gradient mode to be the dominant microinstability in all analysed cases.
The phenomenon of residential segregation was captured by Schelling's famous segregation model where two types of agents are placed on a grid and an agent is content with her location if the fraction of her neighbors which have the same type as her is at least τ , for some 0 < τ < 1. Discontent agents simply swap their location with a randomly chosen other discontent agent or jump to a random empty cell.We analyze a generalized game-theoretic model of Schelling segregation which allows more than two agent types and more general underlying graphs modeling the residential area. For this we show that both aspects heavily influence the dynamic properties and the tractability of finding an optimal placement. We map the boundary of when improving response dynamics (IRD), i.e., the natural approach for finding equilibrium states, are guaranteed to converge. For this we prove several sharp threshold results where guaranteed IRD convergence suddenly turns into the strongest possible non-convergence result: a violation of weak acyclicity. In particular, we show such threshold results also for Schelling's original model, which is in contrast to the standard assumption in many empirical papers. Furthermore, we show that in case of convergence, IRD find an equilibrium in O(m) steps, where m is the number of edges in the underlying graph and show that this bound is met in empirical simulations starting from random initial agent placements.
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