All-Conjugated Polymer Core-Shell and Core-Shell-Shell Particles with Tunable Emission Profiles and White Light Emission

Future applications of conjugated polymer particles (CPP) in medicine, organic photonics, and optoelectronics greatly depend on high performance and precisely adjustable optical properties of the particles. To meet these criteria, current particle systems often combine conjugated polymers with inorganic particles in core-shell geometries, extending the possible optical characteristics of CPP. However, current conjugated polymer particles are restricted to a single polymer phase composed of a distinct polymer or a polymer blend. Here, a synthetic toolbox is presented that enables the synthesis of monodisperse core-shell and core-shell-shell particles, which consist entirely of conjugated polymers but of different types in the core and the shells. Seeded and fed-batch dispersion polymerizations based on Suzuki-Miyaura-type cross-coupling are investigated. The different approaches allow accurate control over the created interface between the conjugated polymer phases and thus also over the energy transfer phenomena between them. This approach opens up completely new synthetic freedom for fine tuning of the optical properties of CPP, enabling, for example, the synthesis of individual white light-emitting particles

The Northern Calcareous Alps revisited: Formation of a hyperextended margin and mantle exhumation in the Northern Calcareous Alps sector of the Neo-Tethys (Eastern Alps, Austria)

The Neo-Tethys margin evolution is preserved in the Northern Calcareous Alps (Eastern Alps), from Late Permian crustal stretching to Late Triassic oceanization. The Northern Calcareous Alps represent the salt-floored fold-and-thrust belt developed from the salt-influenced Triassic carbonate sedimentary cover of the ancestral European margin of the Neo-Tethys Ocean. A crustal scale model for the margin has been obtained by restoration of regional cross-sections of the Northern Calcareous Alps carbonate platforms. Lithospheric break-up was investigated from remnants of exhumed mantle found within an evaporitic melange, suggesting hyperextended crust underneath the distal Triassic platforms of the Northern Calcareous Alps preceding breakup. By modelling the thermal evolution of the margin in combination with excellent stratigraphic control, a detailed timeline has been established for the evolution of the Neo-Tethys margin, especially around the period of rapid mantle exhumation. Our study indicates that salt-floored carbonate shelfs can be used as a proxy to characterize the margins evolution, from crustal stretching to continental breakup. Diagnostic stratigraphic records are preserved in the carbonate platforms: pre- mantle exhumation carbonates are represented by aggrading isolated carbonate platforms first, followed by expanding and margin wide prograding carbonate shelfs once thermal subsidence dominates. In addition, a distinct clastic sequence is deposited as an immediate response to mantle exhumation, in between the pre- and post-mantle exhumation carbonate factory. Our study proposes a new refined model for the formation of the Neo-Tethys margin and provides new insights for the dynamic coupling of salt-controlled carbonate shelfs and the underlying lithosphere during continental breakup

All‐Organic Battery Based on Deep Eutectic Solvent and Redox‐Active Polymers

Sustainable battery concepts are of great importance for the energy storage demands of the future. Organic batteries based on redox-active polymers are one class of promising storage systems to meet these demands, in particular when combined with environmentally friendly and safe electrolytes. Deep Eutectic Solvents (DESs) represent a class of electrolytes that can be produced from sustainable sources and exhibit in most cases no or only a small environmental impact. Because of their non-flammability, DESs are safe, while providing an electrochemical stability window almost comparable to established battery electrolytes and much broader than typical aqueous electrolytes. Here, we report the first all-organic battery cell based on a DES electrolyte, which in this case is composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA) alongside the electrode active materials poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) and crosslinked poly(vinylbenzylviologen) (X-PVBV$^{2+}$). The resulting cell shows two voltage plateaus at 1.07 V and 1.58 V and achieves Coulombic efficiencies of 98 %. Surprisingly, the X-PVBV/X-PVBV$^+$ redox couple turned out to be much more stable in NaTFSI : NMA 1 : 6 than the X-PVBV$^+$/X-PVBV$^{2+}$ couple, leading to asymmetric capacity fading during cycling tests

Combining Deep Eutectic Solvents with TEMPO‐based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance

For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity

Stochastic slowdown in evolutionary processes

We examine birth--death processes with state dependent transition probabilities and at least one absorbing boundary. In evolution, this describes selection acting on two different types in a finite population where reproductive events occur successively. If the two types have equal fitness the system performs a random walk. If one type has a fitness advantage it is favored by selection, which introduces a bias (asymmetry) in the transition probabilities. How long does it take until advantageous mutants have invaded and taken over? Surprisingly, we find that the average time of such a process can increase, even if the mutant type always has a fitness advantage. We discuss this finding for the Moran process and develop a simplified model which allows a more intuitive understanding. We show that this effect can occur for weak but non--vanishing bias (selection) in the state dependent transition rates and infer the scaling with system size. We also address the Wright-Fisher model commonly used in population genetics, which shows that this stochastic slowdown is not restricted to birth-death processes.Comment: 8 pages, 3 figures, accepted for publicatio

Conjugated Polyimidazole Nanoparticles as Biodegradable Electrode Materials for Organic Batteries

Conjugated polymers are promising active materials for batteries. Batteries not only need to have high energy density but should also combine safe handling with recyclability or biodegradability after reaching their end-of-life. Here, π-conjugated polyimidazole particles are developed, which are prepared using atom economic direct arylation adapted to a dispersion polymerization protocol. The synthesis yields polyimidazole nanoparticles of tunable size and narrow dispersity. In addition, the degree of crosslinking of the polymer particles can be controlled. It is demonstrated that the polyimidazole nanoparticles can be processed together with carbon black and biodegradable carboxymethyl cellulose binder as an active material for organic battery electrodes. Electrochemical characterization shows that a higher degree of crosslinking significantly improves the electrochemical performance and leads to clearer oxidation and reduction signals of the polymer. Polyimidazole as part of the composite electrode shows complete degradation by exposure to composting bacteria over the course of 72 h

Cardiovascular magnetic resonance myocardial feature tracking detects quantitative wall motion during dobutamine stress

Contains fulltext : 96698.pdf (publisher's version ) (Open Access)BACKGROUND: Dobutamine stress cardiovascular magnetic resonance (DS-CMR) is an established tool to assess hibernating myocardium and ischemia. Analysis is typically based on visual assessment with considerable operator dependency. CMR myocardial feature tracking (CMR-FT) is a recently introduced technique for tissue voxel motion tracking on standard steady-state free precession (SSFP) images to derive circumferential and radial myocardial mechanics.We sought to determine the feasibility and reproducibility of CMR-FT for quantitative wall motion assessment during intermediate dose DS-CMR. METHODS: 10 healthy subjects were studied at 1.5 Tesla. Myocardial strain parameters were derived from SSFP cine images using dedicated CMR-FT software (Diogenes MRI prototype; Tomtec; Germany). Right ventricular (RV) and left ventricular (LV) longitudinal strain (EllRV and EllLV) and LV long-axis radial strain (ErrLAX) were derived from a 4-chamber view at rest. LV short-axis circumferential strain (EccSAX) and ErrSAX; LV ejection fraction (EF) and volumes were analyzed at rest and during dobutamine stress (10 and 20 mug . kg(1). min(1)). RESULTS: In all volunteers strain parameters could be derived from the SSFP images at rest and stress. EccSAX values showed significantly increased contraction with DSMR (rest: -24.1 +/- 6.7; 10 mug: -32.7 +/- 11.4; 20 mug: -39.2 +/- 15.2; p < 0.05). ErrSAX increased significantly with dobutamine (rest: 19.6 +/- 14.6; 10 mug: 31.8 +/- 20.9; 20 mug: 42.4 +/- 25.5; p < 0.05). In parallel with these changes; EF increased significantly with dobutamine (rest: 56.9 +/- 4.4%; 10 mug: 70.7 +/- 8.1; 20 mug: 76.8 +/- 4.6; p < 0.05). Observer variability was best for LV circumferential strain (EccSAX ) and worst for RV longitudinal strain (EllRV) as determined by 95% confidence intervals of the difference. CONCLUSIONS: CMR-FT reliably detects quantitative wall motion and strain derived from SSFP cine imaging that corresponds to inotropic stimulation. The current implementation may need improvement to reduce observer-induced variance. Within a given CMR lab; this novel technique holds promise of easy and fast quantification of wall mechanics and strain