Water‐soluble, and ferrocene‐containing methacrylamide copolymers with different comonomer ratios of the solubility‐promoting comonomer [2‐(methacryloyloxy)‐ethyl]‐trimethylammonium chloride (METAC) are synthesized in order to obtain a novel, temperature‐stable electrolyte for aqueous redox flow batteries. The electrochemical properties of one chosen polymer are studied in detail by cyclic voltammetry and rotating disc electrode (RDE) investigations. Additionally, the diffusion coefficient and the charge transfer rate are obtained from these measurements. The diffusion coefficient from RDE is compared to the value from synthetic boundary experiments at battery concentrations, using an analytical ultracentrifuge, yielding diffusion coefficients of a similar order of magnitude. The polymer is further tested in a redox flow battery setup. While performing charge and discharge experiments against the well‐established bis‐(trimethylammoniumpropyl)‐viologen, the polymer reveals high columbic efficiencies of >99.8% and desirable apparent capacity retention, both at room temperature as well as at 60 °C. Further experiments are conducted to verify the stability of the active compounds under these conditions in both charge states. Lastly, the electrochemical behavior is linked to the characteristics of the polymers concerning absolute values of the molar mass and diffusion coefficients.
Cationic polymers play a crucial role within the field of gene delivery offering the possibility to circumvent (biological) barriers in an elegant way. However, polymers are accompanied either by a high cytotoxicity or low efficiency. In this study, a series of high molar mass poly(2-oxazoline)-based copolymers was synthesized introducing 2-ethyl-2-oxazoline, ethylene imine, and primary amine bearing monomer units representing a new generation of poly(ethylene imine) (PEI). The potential of these modified PEIs as non-viral gene delivery agents was assessed and compared to linear PEI by studying the cytotoxicity, the polyplex characteristics, the transfection efficiency, and the cellular uptake using plasmid DNA (pDNA) as well as small interfering RNA (siRNA). High transfection efficiencies, even in serum containing media, were achieved using pDNA without revealing any cytotoxic effects on the cell viability at concentrations up to 1 mg mL−1. The delivery potential for siRNA was further investigated showing the importance of polymer composition for different genetic materials. To elucidate the origins for this superior performance, super-resolution and electron microscopy of transfected cells were used, identifying the endosomal release of the polymers as well as a reduced protein interaction as the main difference to PEI-based transfection processes. In this respect, the investigated copolymers represent remarkable alternatives as non-viral gene delivery agents.
In this work, two new redox-active ionic liquids, one based on 2,2,6,6-tetramethylpiperidine-N-oxide and the other based on 4,4′-bipyridine, are synthesized and characterized. A ferrocene-based redox-active ionic liquid is used for referencing the results. All ionic liquids are formed via salt-metathesis from halogenate to bis(trifluoromethylsulfonyl)imide. Their fundamental thermal characteristics are assessed with differential scanning calorimetry. While the imidazolium ionic liquids show no melting point, the phase transition is well observable for the viologen-based ionic liquid. The properties of the neat redox-active ionic liquids and of binary mixtures containing these ionic liquids (0.1 m) and 1-butyl-1-methyl pyrrolidinium-bis(trifluoromethylsulfonyl)imide have been investigated. Finally, the use of these binary mixtures in combination with activated carbon-based electrodes has been considered in view of the use of these redox-active electrolytes in supercapacitors.
A novel monomer, 2-ferrocene-ethyl-2-oxazoline, was copolymerized with 2-alkyl-2-oxazolines. The resulting well-defined polymers retained the reversible redox-activity of ferrocene, thus proving the absence of any unfavorable side reactions.