Publikationen

Microporous carbonaceous electrode materials store charge by ion electrosorption onto the electrode surface. Despite significant efforts to understand this phenomenon, a definitive picture of the adsorption mechanisms within these complex nanoscale structures is lacking. Here, we use nuclear magnetic resonance (NMR) spectroscopy to directly observe and quantify aqueous adsorbate partitioning behavior driven by spontaneous physisorption within the micropores. Our results show that the solvation properties of the electrolyte ions influence the ionophilicity/ionophobicity of the adsorbate-carbon system, with ionophilic and ionophobic systems exhibiting distinct behavior concerning the electrolyte loading volume. Micropore diameter is also shown to influence spontaneous electrolyte partitioning behavior and disturb ion solvation. In situ NMR spectroscopy using a working supercapacitor comprising microporous carbon electrodes with aqueous sodium sulfate and aqueous sodium bis(trifluoromethane)sulfonimide electrolytes indicates that spontaneous electrolyte partitioning behavior influences the charge-balancing mechanism. Our results suggest that spontaneously ionophilic systems favor charge-balancing by counter-ion adsorption under an applied voltage, and spontaneously ionophobic systems favor a co-ion ejection mechanism under an applied potential. These results provide new molecular-level insight into the role of electrolyte properties on spontaneous physisorption behavior and charged electrosorption behavior within microporous carbon electrodes.

Glycerol is a widely used signaling bioanalyte in biotechnology. Glycerol can serve as a substrate or product of many metabolic processes in cells. Therefore, quantification of glycerol in fermentation samples with inexpensive, reliable, and rapid sensing systems is of great importance. In this work, an amperometric assay based on one-step designed electroplated functional Pd layers with controlled design was proposed for a rapid and selective measurement of glycerol in yeast fermentation medium. A novel assay utilizing electroplated Pd-sensing layers allows the quantification of glycerol in yeast fermentation medium in the presence of interfering species with RSD below 3% and recoveries ranged from 99 to 103%. The assay requires minimal sample preparation, viz. adjusting of sample pH to 12. The time taken to complete the electrochemical analysis was 3 min. Remarkably, during investigations, it was revealed that sensitivity and selectivity of glycerol determination on Pd sensors were significantly affected by its adsorption and did not depend on the surface structure of sensing layers. This study is expected to contribute to both fundamental and practical research fields related to a preliminary choice of functional sensing layers for specific biotechnology and life science applications in the future.

Mechanical metamaterials are known for their prominent mechanical characteristics such as programmable deformation that are due to periodic microstructures. Recent research trends have shifted to utilizing mechanical metamaterials as structural substrates to integrate with functional materials for advanced functionalities beyond mechanical, such as active sensing. This study reports on the ultra-stretchable kirigami piezo-metamaterials (KPM) for sensing coupled large deformations caused by in- and out-of-plane displacements using the lead zirconate titanate (PZT) and barium titanate (BaTiO3) composite films. The KPM are fabricated by uniformly compounding and polarizing piezoelectric particles (i.e., PZT and BaTiO3) in silicon rubber and structured by cutting the piezoelectric rubbery films into ligaments. Characterizes the electrical properties of the KPM and investigates the bistable mechanical response under the coupled large deformations with the stretching ratio up to 200% strains. Finally, the PZT KPM sensors are integrated into wireless sensing systems for the detection of vehicle tire bulge, and the non-toxic BaTiO3 KPM are applied for human posture monitoring. The reported kirigami piezo-metamaterials open an exciting venue for the control and manipulation of mechanically functional metamaterials for active sensing under complex deformation scenarios in many applications.

Synthetic cells can advance immunotherapy, offering innovative approaches to understanding and enhancing immune responses. This review article delves into the advancements and potential of synthetic cell technologies in immunology, emphasizing their role in understanding and manipulating immune functions. Recent progress in understanding vertebrate immune systems and the challenges posed by diseases highlight the need for innovative research methods, complementing the analysis of multidimensional datasets and genetic engineering. Synthetic immune cell engineering aims to simplify the complexity of immunological systems by reconstructing them in a controlled setting. This approach, alongside high-throughput strategies, facilitates systematic investigations into immunity and the development of novel treatments. The article reviews synthetic cell technologies, focusing on their alignment with the three laws of immunity: universality, tolerance, and appropriateness. It explores the integration of synthetic cell modules to mimic processes such as controlled T-cell activation, bacteria engulfment and elimination, or cellular maturation into desirable phenotypes. Together, such advancements expand the toolbox for understanding and manipulating immune functions. Synthetic cell technologies stand at the innovation crossroads in immunology, promising to illuminate fundamental immune system principles and open new avenues for research and therapy.

Treatment of microbial infections is becoming daunting because of widespread antimicrobial resistance. The treatment challenge is further exacerbated by the fact that certain infectious bacteria invade and localize within host cells, protecting the bacteria from antimicrobial treatments and the host’s immune response. To survive in the intracellular niche, such bacteria deploy surface receptors similar to host cell receptors to sequester iron, an essential nutrient for their virulence, from host iron-binding proteins, in particular lactoferrin and transferrin. In this context, we aimed to target lactoferrin receptors expressed by macrophages and bacteria; as such, we prepared and characterized lactoferrin nanoparticles (Lf-NPs) loaded with a dual drug combination of antimicrobial natural alkaloids, berberine or sanguinarine, with vancomycin or imipenem. We observed increased uptake of drug-loaded Lf-NPs by differentiated THP-1 cells with up to 90% proportion of fluorescent cells, which decreased to about 60% in the presence of free lactoferrin, demonstrating the targeting ability of Lf-NPs. The encapsulated antibiotic drug cocktail efficiently cleared intracellular Staphylococcus aureus (Newman strain) compared to the free drug combinations. However, the encapsulated drugs and the free drugs alike exhibited a bacteriostatic effect against the hard-to-treat Mycobacterium abscessus (smooth variant). In conclusion, the results of this study demonstrate the potential of lactoferrin nanoparticles for the targeted delivery of antibiotic drug cocktails for the treatment of intracellular bacteria.

Li–S batteries with an improved cycle life of over 1000 cycles have been achieved using cathodes of sulfur-infiltrated nanoporous carbon with carbonate-based electrolytes. In these cells, a protective cathode–electrolyte interphase (CEI) is formed, leading to solid-state conversion of S to Li2S in the nanopores. This prevents the dissolution of polysulfides and slows capacity fade. However, there is currently little understanding of what limits the capacity and rate performance of these Li–S batteries. Here, we aim to deepen our understanding of the capacity and rate limitation using a variety of structure-sensitive and electrochemical techniques, such as operando small-angle neutron scattering (SANS), operando X-ray diffraction (XRD), electrochemical impedance spectroscopy, and galvanostatic charge/discharge. Operando SANS and XRD data give direct evidence of CEI formation and solid-state sulfur conversion occurring inside the nanopores. Electrochemical measurements using two nanoporous carbons with different pore sizes suggest that charge transfer at the active material interfaces and the specific CEI/active material structure in the nanopores play the dominant role in defining capacity and rate performance. This work helps define strategies to increase the sulfur loading while maximizing sulfur usage, rate performance, and cycle life.

Peptide drugs have seen rapid advancement in biopharmaceutical development, with over 80 candidates approved
globally. Despite their therapeutic potential, the clinical translation of peptide drugs is hampered by challenges
in production yields and stability. Engineered bacterial therapeutics is a unique approach being explored to overcome
these issues by using bacteria to produce and deliver therapeutic compounds at the body site of use. A key advan‑
tage of this technology is the possibility to control drug delivery within the body in real time using genetic switches.
However, the performance of such genetic switches suffers when used to control drugs that require post‑translational
modifications or are toxic to the host. In this study, these challenges were experienced when attempting to establish
a thermal switch for the production of a ribosomally synthesized and post‑translationally modified peptide antibiotic,
darobactin, in probiotic E. coli. These challenges were overcome by developing a thermo‑amplifier circuit that com‑
bined the thermal switch with a T7 RNA Polymerase. Due to the orthogonality of the Polymerase, this strategy
overcame limitations imposed by the host transcriptional machinery. This circuit enabled production of pathogen‑
inhibitory levels of darobactin at 40 °C while maintaining leakiness below the detection limit at 37 °C. Furthermore,
the thermo‑amplifier circuit sustained gene expression beyond the thermal induction duration such that with only
2 h of induction, the bacteria were able to produce pathogen‑inhibitory levels of darobactin. This performance
was maintained even in physiologically relevant simulated conditions of the intestines that include bile salts and low
nutrient levels

In engineered living materials (ELMs) non-living matrices encapsulate microorganisms to acquire capabilities like sensing or biosynthesis. The confinement of the organisms to the matrix and the prevention of overgrowth and escape during the lifetime of the material is necessary for the application of ELMs into real devices. In this study, a bilayer thin film hydrogel of Pluronic F127 and Pluronic F127 acrylate polymers supported on a solid substrate is introduced. The inner hydrogel layer contains genetically engineered bacteria and supports their growth, while the outer layer acts as an envelope and does not allow leakage of the living organisms outside of the film for at least 15 days. Due to the flat and transparent nature of the construct, the thin layer is suited for microscopy and spectroscopy-based analyses. The composition and properties of the inner and outer layer are adjusted independently to fulfil viability and confinement requirements. We demonstrate that bacterial growth and light-induced protein production are possible in the inner layer and their extent is influenced by the crosslinking degree of the used hydrogel. Bacteria inside the hydrogel are viable long term, they can act as lactate-sensors and remain active after storage in phosphate buffer at room temperature for at least 3 weeks. The versatility of bilayer bacteria thin-films is attractive for fundamental studies and for the development of application-oriented ELMs.

Engineered living materials (ELMs) encapsulate microorganisms within polymeric matrices for biosensing, drug delivery, capturing viruses, and bioremediation. It is often desirable to control their function remotely and in real time and so the microorganisms are often genetically engineered to respond to external stimuli. Here, we combine thermogenetically engineered microorganisms with inorganic nanostructures to sensitize an ELM to near infrared light. For this, we use plasmonic gold nanorods (AuNR) that have a strong absorption maximum at 808 nm, a wavelength where human tissue is relatively transparent. These are combined with Pluronic-based hydrogel to generate a nanocomposite gel that can convert incident near infrared light into heat locally. We perform transient temperature measurements and find a photothermal conversion efficiency of 47 %. Steady-state temperature profiles from local photothermal heating are quantified using infrared photothermal imaging and correlated with measurements inside the gel to reconstruct spatial temperature profiles. Bilayer geometries are used to combine AuNR and bacteria-containing gel layers to mimic core-shell ELMs. The thermoplasmonic heating of an AuNR-containing hydrogel layer that is exposed to infrared light diffuses to the separate but connected hydrogel layer with bacteria and stimulates them to produce a fluorescent protein. By tuning the intensity of the incident light, it is possible to activate either the entire bacterial population or only a localized region.

Herein, a rapid electrochemical screening of yeasts (Saccharomyces cerevisiae) in vitro mode depending on their optical density, cultivation time and growth medium used was conducted in 3 min by palladium nanoparticles (Pd-NPs)-modified electrodes. Pd-NPs-modified electrodes operated in cyclic voltammetry mode at low scan rates, i.e. 5–20 mV/s supported a low oxidative process in the yeast extracellular matrix. The electrochemical screening relied on an efficient electrooxidation of secondary metabolites, i.e. organohydrazines formed in the extracellular medium as a result of microbial activity of yeast cells. More importantly, during the study the impact of fundamental parameters, viz. type of the matrix and pH on electroanalytical response of Pd-NPs-based electrodes in real fermentation medium was investigated in detail. The efficiency of the proposed in vitro electrochemical screening of yeast extracellular matrix was not affected by pH of the samples or composition of the multicomponent medium, but more likely exclusively depended on the presence of organohydrazines. The potential of this electroanalytical approach towards profiling of the extracellular matrix of Saccharomyces cerevisiae was compared with results obtained by gas chromatography mass-spectrometry (GC–MS) and genetically encoded biosensor (ro-GFP2) assays.