Publikationen

There is an increasing interest in coupling reactions for cross-linking of cell-encapsulating hydrogels under biocompatible, chemoselective, and tunable conditions. Inspired by the biosynthesis of luciferins in fireflies, here we exploit the cyanobenzothiazole-cysteine (CBT-Cys) click ligation to develop polyethylene glycol hydrogels as tunable scaffolds for cell encapsulation. Taking advantage of the chemoselectivity and versatility of CBT-Cys ligation, a highly flexible gel platform is reported here. We demonstrate luciferin-inspired hydrogels with important advantages for cell encapsulation applications: (i) gel precursors derived from inexpensive reagents and with good stability in aqueous solution (>4 weeks), (ii) adjustable gel mechanics within physiological ranges (E = 180–6240 Pa), (iii) easy tunability of the gelation rate (seconds to minutes) by external means, (iv) high microscale homogeneity, (v) good cytocompatibility, and (iv) regulable biological properties. These flexible and robust CBT-Cys hydrogels are proved as supportive matrices for 3D culture of different cell types, namely, fibroblasts and human mesenchymal stem cells. Our findings expand the toolkit of click chemistries for the fabrication of tunable biomaterials.

Endothelial cells play a central role in the vascular system, where their function is tightly regulated by both cell-extracellular matrix (e.g., via integrins) and cell–cell interactions (e.g., via cadherins). In this study, we incorporated cholesterol-modified integrin and N-cadherin peptide binding ligands in fluid supported lipid bilayers. Human umbilical vein endothelial cell adhesion, spreading and vinculin localization in these cells were dependent on ligand density. One composition led to observe a higher extent of cell spreading, where cells exhibited extensive lamellipodia formation and a qualitatively more distinct N-cadherin localization at the cell periphery, which is indicative of N-cadherin clustering and a mimic of cell–cell contact formation. The results can be used to reconstitute the endothelial-pericyte interface on biomedical devices and materials.

The opto-electronic properties of small-molecules and functional dyes usually differ when incorporated into solid matrices with respect to their isolated form due to an aggregation phenomenon that alters their optical and fluorescent properties. These spectroscopic modifications are studied in the framework of the exciton theory of aggregates, which has been extensively applied in the literature for the study of molecular aggregates of the same type of molecules (homoaggregation). Despite the demonstrated potential of the control of the heteroaggregation process (aggregation of different types of molecules), most of the reported works are devoted to intramolecular aggregates, complex molecules formed by several chromophores attached by organic linkers. The intramolecular aggregates are specifically designed to hold a certain molecular structure that, on the basis of the exciton theory, modifies their optical and fluorescent properties with respect to the isolated chromophores that form the molecule. The present article describes in detail the incorporation of Rhodamine 6G (Rh6G) and 800 (Rh800) into polymeric matrices of poly-(methyl methacrylate), PMMA. The simultaneous incorporation of both dyes results in an enhanced fluorescent emission in the near-infrared (NIR), originating from the formation of ground-state Rh6G–Rh800 intermolecular heteroaggregates. The systematic control of the concentration of both rhodamines provides a model system for the elucidation of the heteroaggregate formation. The efficient energy transfer between Rh6G and Rh800 molecules can be used as wavelength shifters to convert effectively the light from visible to NIR, a very convenient wavelength range for many practical applications which make use of inexpensive commercial detectors and systems.

Seawater batteries are unique energy storage systems for sustainable renewable energy storage by directly utilizing seawater as a source for converting electrical energy and chemical energy. This technology is a sustainable and cost-effective alternative to lithium-ion batteries, benefitting from seawater-abundant sodium as the charge-transfer ions. Research has significantly improved and revised the performance of this type of battery over the last few years. However, fundamental limitations of the technology remain to be overcome in future studies to make this method even more viable. Disadvantages include degradation of the anode materials or limited membrane stability in aqueous saltwater resulting in low electrochemical performance and low Coulombic efficiency. The use of seawater batteries exceeds the application for energy storage. The electrochemical immobilization of ions intrinsic to the operation of seawater batteries is also an effective mechanism for direct seawater desalination. The high charge/discharge efficiency and energy recovery make seawater batteries an attractive water remediation technology. Here, the seawater battery components and the parameters used to evaluate their energy storage and water desalination performances are reviewed. Approaches to overcoming stability issues and low voltage efficiency are also introduced. Finally, an overview of potential applications, particularly in desalination technology, is provided.

Batteries employing transition-metal sulfides enable high-charge storage capacities, but polysulfide shuttling and volume expansion cause structural disintegration and early capacity fading. The design of heterostructures combining metal sulfides and carbon with an optimized morphology can effectively address these issues. Our work introduces dopamine-coated copper Prussian blue (CuPB) analogue as a template to prepare nanostructured mixed copper–iron sulfide electrodes. The material was prepared by coprecipitation of CuPB with in situ dopamine polymerization, followed by thermal sulfidation. Dopamine controls the particle size and favors K-rich CuPB due to its polymerization mechanism. While the presence of the coating prevents particle agglomeration during thermal sulfidation, its thickness demonstrates a key effect on the electrochemical performance of the derived sulfides. After a two-step activation process during cycling, the C-coated KCuFeS2 electrodes showed capacities up to 800 mAh/g at 10 mA/g with nearly 100% capacity recovery after rate handling and a capacity of 380 mAh/g at 250 mA/g after 500 cycles.

Due to their versatile properties and excellent electrical conductivity, MXenes have become attractive materials for alkali metal-ion batteries. However, as the capacity is limited to lower values due to the intercalation mechanism, these materials can hardly keep up in the ever-fast-growing community of battery research. Antimony has a promisingly high theoretical sodiation capacity characterized by an alloying reaction. The main drawback of this type of battery material is related to the high volume changes during cycling, often leading to electrode cracking and pulverization, resulting in poor electrochemical performance. A synergistic effect of combing antimony and MXene can be expected to obtain an optimized electrochemical system to overcome capacity fading of antimony while taking advantage of MXene charge storage ability. In this work, variation of the synthesis parameters and material design strategy have been dedicated to achieving the optimized antimony/MXene hybrid electrodes for high-performance sodium-ion batteries. The optimized performance does not align with the highest amount of antimony, the smallest nanoparticles, or the largest interlayer distance of MXene but with the most homogeneous distribution of antimony and MXene while both components remain electrochemically addressable. As a result, the electrode with 40 mass% MXene, not previously expanded, etched with 5 mass% HF and 60% antimony synthesized on the surfaces of MXene emerged as the best electrode. We obtained a high reversible capacity of 450 mA h g−1 at 0.1 A g−1 with a capacity retention of around 96% after 100 cycles with this hybrid material. Besides the successful cycling stability, this material also exhibits high rate capability with a capacity of 365 mA h g−1 at 4 A g−1. In situ XRD measurements and post mortem analysis were used to investigate the reaction mechanism.

In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.

Semiconductor materials demonstrate promising potential for wastewater treatment due to their photocatalytic properties, which can be controlled through the design of the bandgap structure. The photogenerated electron and hole in semiconductor materials provide efficient oxidation/reduction performance for the degradation of pollutants, either directly or indirectly, through the generation of reactive species. Photocatalytic degradation has been utilized to treat contaminants ranging from dyes, chemical precursors, and pharmaceuticals, to diverse organic and inorganic waste. Over the past few years, advances in functional materials have achieved wider light absorption ranges and extended charge carrier lifetime through the doping of heteroatoms or the formation of heterojunctions. Despite these advances, innovative strategies are required to target emerging contaminants with environmental persistence, such as perfluorinated compounds, and improve the efficiency of these nanomaterials in real water matrices in the presence of multicomponent interfering ions. In this review, recent advances on the application of semiconductor catalysts for wastewater treatment and environmental remediation are reviewed, and new approaches that may overcome the current limitations are discussed.

Mixed-metal oxides (MMOx), oxides with more than one (transition) metal, provide versatile structural and electrochemical properties well exploited in energy conversion and electrochemical energy storage. The preparation of MMOx from single-source precursors benefits from homogeneous composition and uniform metal distribution. Herein, we describe layered mixed-metal carbides (MXenes) as templates to prepare MMOx. Through thermal oxidation of TiNb-based MXenes in CO2, mixtures of Ti and Nb oxides were produced. The Ti-to-Nb ratio in the MXene significantly affects the derived oxide composition but does not show a direct stoichiometric relation between them. At higher Ti ratios, oxide mixtures of TiO2 and titanium niobium oxide are obtained, while with Nb excess, only MMOx are produced. Multilayer MXenes retain carbon upon oxidation and produce TiNbOx/C hybrids, while delaminated MXenes lead to pure TiNbOx. When tested as Li-ion battery electrodes, the multilayer MXene-derived MMOx with Ti/Nb = 1:5 presented 226 mAh·g–1 at 10 mA·g–1 and 75% retention after 1000 cycles at 1 A·g–1.