Scientific publications

This study concerns the development of sustainable design strategies of aqueous electrolytes for redox flow batteries using redox-active organic materials. A green spontaneous grafting reaction occurs between a redox-active organic radical and an electrochemically activated structural modifier at room temperature through a simple mixing step. Then, a physical mixing method is used to formulate a structured aqueous electrolyte and enables aqueous solubilization of the organic solute from below 0.5 to 1.5 m beyond the conventional dissolution limit. The as-obtained concentrated mixture can be readily used as catholyte for a redox flow battery. A record high discharge cell voltage (1.6 V onset output voltage) in aqueous non-hybrid flow cell is attained by using the studied electrolytes.

Continuous and distributed monitoring of environmental parameters may pave the way for developing sustainable strategies to tackle climate challenges. State-of-the-art technologies, made with electronic systems, are often costly, heavy, and generate e-waste. Here, we propose a new generation of self-deployable, biocompatible, and luminescent artificial flying seeds for wireless, optical, and eco-friendly monitoring of environmental parameters (i.e., temperature). Inspired by natural Acer campestre plant seeds, we developed three-dimensional functional printed luminescent seed–like fliers, selecting polylactic acid as a biocompatible matrix and temperature as a physical parameter to be monitored. The artificial seeds mimic the aerodynamic and wind dispersal performance of the natural ones. The sensing properties are given by the integration of fluorescent lanthanide–doped particles, whose photoluminescence properties depend on temperature. The luminescent artificial flying seeds can be optically read from a distance using eye-safe near-infrared wavelengths, thus acting as a deployable sensor for distributed monitoring of topsoil environmental temperatures.

Self-healing nanocomposites can be generated by organic functionalization of inorganic nanoparticles and complementary functionalization of the polymer matrix, allowing reversible interactions between the two components. Here, we report on self-healing nanocomposites based on ionic interactions between anionic copolymers consisting of di(ethylene glycol) methyl ether methacrylate, sodium 4-(methacryloyloxy)butan-1-sulfonate, and cationically functionalized iron oxide nanoparticles. The materials exhibited hygroscopic behavior. At water contents < 6%, the shear modulus was reduced by up to 90%. The nanoparticle concentration was identified as a second factor strongly influencing the mechanical properties of the materials. Backscattered scanning electron microscopy and small-angle X-ray scattering measurements showed the formation of agglomerates in the size range of 100 nm to a few µm in diameter, independent of concentration, resulting in the disordering of the semi-crystalline ionic polymer blocks. These effects resulted in an increase in the shear modulus of the composite from 3.7 MPa to 5.6 MPa, 6.3 Mpa, and 7.5 MPa for 2, 10, and 20 wt% particles, respectively. Temperature-induced self-healing was possible for all composites investigated. However, only 36% of the maximum stress could be recovered in systems with a low nanoparticle content, whereas the original properties were largely restored (>85%) at higher particle contents.

Ionic liquids are attractive liquid materials for many advanced applications. For targeted design, in-depth knowledge about their structure–property-relations is urgently needed. We prepared a set of novel protic ionic liquids (PILs) with a guanidinium cation with either an ether or alkyl side chain and different anions. While being a promising cation class, the available data is insufficient to guide design. We measured thermal and transport properties, nuclear magnetic resonance (NMR) spectra as well as liquid and crystalline structures supported by ab initio computations and were able to obtain a detailed insight into the influence of the anion and the ether substitution on the physical and spectroscopic properties. For the PILs, hydrogen bonding is the main interaction between cation and anion and the H-bond strength is inversely related to the proton affinity of the constituting acid and correlated to the increase of 1H and 15N chemical shifts. Using anions from acids with lower proton affinity leads to proton localization on the cation as evident from NMR spectra and self-diffusion coefficients. In contrast, proton exchange was evident in ionic liquids with triflate and trifluoroacetate anions. Using imide-type anions and ether side groups decreases glass transitions as well as fragility, and accelerated dynamics significantly. In case of the ether guanidinium ionic liquids, the conformation of the side chain adopts a curled structure as the result of dispersion interactions, while the alkyl chains prefer a linear arrangement.

Ionic liquids are modern materials with a broad range of applications, including electrochemical devices, the exploitation of sustainable resources and chemical processing. Expanding the chemical space to include novel ion classes allows for the elucidation of novel structure-property relationships and fine tuning for specific applications. We prepared a set of ionic liquids based on the sparsely investigated pentamethyl guanidinium cation with a 2-ethoxy-ethyl side chain in combination with a series of frequently used anions. The resulting properties are compared to a cation with a pentyl side chain lacking ether functionalization. We measured the thermal transitions and transport properties to estimate the performance and trends of this cation class. The samples with imide-type anions form liquids at ambient temperature, and show good transport properties, comparable to imidazolium or ammonium ionic liquids. Despite the dynamics being significantly accelerated, ether functionalization of the cation favors the formation of crystalline solids. Single crystal structure analysis, ab initio calculations and variable temperature nuclear magnetic resonance measurements (VT-NMR) revealed that cation conformations for the ether- and alkyl-chain-substituted are different in both the solid and liquid states. While ether containing cations adopt compact, curled structures, those with pentyl side chains are linear. The Eyring plot revealed that the curled conformation is accompanied by a higher activation energy for rotation around the carbon-nitrogen bonds, due to the coordination of the ether chain as observed by VT-NMR.

One of the major limitations of flexible sensors is the loss of conductivity upon multiple stretching and bending cycles. Conducting fillers with two different geometries, carbon black and carbon nanotubes, were introduced in polydimethylsiloxane (PDMS) for physical insights into the structure formation of nanofillers by the application of periodic tensile stress. The loading of the nanofillers was selected beyond the percolation threshold to determine the cyclic stability of the resulting network channels. The surface chemistry of carbon nanotubes has been varied to understand the interfacial interactions at the molecular length scale. The combination of in situ stretching, annealing, and vis-à-vis conductometry of nanocomposite films with synchrotron-based ultra-small angle X-ray scattering experiments enables us to highlight the importance of the fractal dimensions of nanofillers for the molecular level interactions. The irreversible formation of nanofiller network geometries under cyclic stress and annealing was found to be responsible for the electrical properties of a flexible conducting film.

The kinetics of a ligand-receptor interaction determine the responses of the receptor-expressing cell. One approach to experimentally and reversibly change this kinetics on demand is optogenetics. We have previously developed a system in which the interaction of a modified receptor with an engineered ligand can be controlled by light. In this system the ligand is a soluble Phytochrome B (PhyB) tetramer and the receptor is fused to a mutated PhyB-interacting factor (PIFS). However, often the natural ligand is not soluble, but expressed as a membrane protein on another cell. This allows ligand-receptor interactions in two dimensions. Here, we developed a strategy to generate cells that display PhyB as a membrane-bound protein by expressing the SpyCatcher fused to a transmembrane domain in HEK-293T cells and covalently coupling purified PhyB-SpyTag to these cells. As proof-of-principle, we use Jurkat T cells that express a GFP-PIFS-T cell receptor and show that these cells can be stimulated by the PhyB-coupled HEK-293T cells in a light dependent manner. Thus, we call the PhyB-coupled cells opto-antigen presenting cells (opto-APCs). Our work expands the toolbox of optogenetic technologies, allowing two-dimensional ligand-receptor interactions to be controlled by light.

Anionic polymerization for the preparation of polystyrene-b-polybutadiene is well-established and leads to thermoplastic elastomers on industrial scale. The classical ABA block copolymer (BCP) architecture and composition usually forms a cylindrical morphology in the bulk state. Their anisotropic mechanical properties are, however, unfavorable for many applications. The gyroid microphase is entirely isotropic, but it is only formed in a narrow compositional area of around 35 vol% of the minority polymer block. In the present study, a second-generation dendrimer-like block copolymer structure ((AB)2B)3 is described. This BCP architecture is expected to show a higher curvature on the microphase boundaries, which leads to a larger morphological range for the gyroid phase. Three compositionally different polymers are synthesized by living anionic polymerization strategies and the resulting morphology is analyzed via transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The dendrimer-like BCPs are compared to their less branched analogues, namely the asymmetric star polymers and H-shape stars. The expected influence of the dendrimer-like BCP architecture on the microphase separation is investigated paving the way to a promising synthetic platform for interesting mechanical and optical properties.

Due to their high energy density, Li-ion batteries have become indispensable for energy storage in many technical devices. Prussian blue and its analogs are a versatile family of materials. Apart from their direct use as an alkali-ion battery electrode, they are a promising source for templating other compounds due to the presence of carbon, nitrogen, and metallic elements in their structure, ease of synthesis, and high tunability. In this study, homogeneous iron vanadate derivatization from iron vanadium Prussian blue was successfully carried out using an energy efficient infrared furnace utilizing CO2 gas. Iron-vanadate is an inherently unstable electrode material if cycled at low potentials vs. Li/Li+. Several parameters were optimized to achieve a stable electrochemical performance of this derivative, and the effect of surfactants, such as tannic acid, sodium dodecylbenzene sulfonate, and polyvinylpyrrolidone were shown with their role in the morphology and electrochemical performance. While stabilizing the performance, we demonstrate that the type and order of addition of these surfactants are fundamental for a successful coating formation, otherwise they can hinder the formation of PBA, which has not been reported previously. Step-by-step, we illustrate how to prepare self-standing electrodes for Li-ion battery cells without using an organic solvent or a fluorine-containing binder while stabilizing the electrochemical performance. A 400 mA h g−1 capacity at the specific current of 250 mA g−1 was achieved after 150 cycles while maintaining a Coulombic efficiency of 99.2% over an extended potential range of 0.01–3.50 V vs. Li/Li+.