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Despite considerable interest in heteroatom-containing conjugated polymers, there are only few examples with heavier p-block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds—albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion-ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). UV/Vis and NMR data confirm the presence of σ,π-conjugation across the silylene-phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder-like cylindrical assemblies as confirmed by X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles.
Life After Death: Re-Purposing End-of-Life Supercapacitors for Electrochemical Water Desalination
(2024)
This study explores the potential of re-purposing end-of-life commercial supercapacitors as electrochemical desalination cells, aligning with circular economy principles. A commercial 500-Farad supercapacitor was disassembled, and its carbon electrodes underwent various degrees of modification. The most straightforward modification involved NaOH-etching of the aluminum current collector to produce free-standing carbon films. More advanced modifications included CO2 activation and binder-added wet processing of the electrodes. When evaluated as electrodes for electrochemical desalination via capacitive deionization of low-salinity (20 mM) NaCl solutions, the minimally modified NaOH-etched carbon electrodes achieved an average desalination capacity of 5.8 mg g−1 and a charge efficiency of 80 %. In contrast, the CO2-activated, wet-processed electrodes demonstrated an improved desalination capacity of 7.9 mg g−1 and a charge efficiency above 90 % with stable performance over 20 cycles. These findings highlight the feasibility and effectiveness of recycling supercapacitors for sustainable water desalination applications, offering a promising avenue for resource recovery and re-purposing in pursuing environmental sustainability.
Skin equivalents (SE) that recapitulate biological and mechanical characteristics of the native tissue are promising platforms for assessing cosmetics and studying fundamental biological processes. Methods to achieve SEs with well-organized structure, and ideal biological and mechanical properties are limited. Here, the combination of melt electrowritten PCL scaffolds and cell-laden Matrigel to fabricate SE is described. The PCL scaffold provides ideal structural and mechanical properties, preventing deformation of the model. The model consists of a top layer for seeding keratinocytes to mimic the epidermis, and a bottom layer of Matrigel-based dermal compartment with fibroblasts. The compressive modulus and the biological properties after 3-day coculture indicate a close resemblance with the native skin. Using the SE, a testing system to study the damage caused by UVA irradiation and evaluate antioxidant efficacy is established. The effectiveness of Tea polyphenols (TPs) and L-ascorbic acid (Laa) is compared based on free radical generation. TPs are demonstrated to be more effective in downregulating free radical generation. Further, T1 relaxometry is used to detect the generation of free radicals at a single-cell level, which allows tracking of the same cell before and after UVA treatment.
The laser welding of Cu–Al alloys for battery applications in the automotive industry presents significant challenges due to the high reflectivity of copper. Inadequate bonding and low mechanical strength may occur when the laser radiation is directed toward the copper side in an overlap configuration welding. To tackle these challenges, a laser surface treatment technique is implemented to enhance the absorption characteristics and overcome the reflective nature of the copper material. However, elevating the surface roughness and heat-energy input over threshold values leads to heightened temperature and extreme weld. This phenomenon escalates the formation of detrimental intermetallic compounds (IMC), creating defects like cracks and porosity. Metallurgical analysis, which is time-consuming and expensive, is usually used in studies to detect these phases and defects. However, to comprehensively evaluate the weld quality and discern the impact of surface structure, adopting a more innovative approach that replaces conventional cross-sectional metallography is essential. This article proposes a model based on the image feature extraction of the welds to study the effect of the laser-based structure and the other laser parameters. It can detect defects and identify the weld quality by weld classification. However, due to the complexity of the photo features, the system requires image processing and a convolutional neural network (CNN). Results show that the predictive model based on trained data can detect different weld categories and recognize unstable welds. The project aims to use a monitoring model to guarantee optimized and high-quality weld series production. To achieve this, a deeper study of the parameters and the microstructure of the weld is utilized, and the CNN model analyzes the features of 1310 pieces of weld photos with different weld parameters.
Recent advances in engineered bacterial therapeutics underscore their potential in treating diseases via targeted, live interventions. Despite their promising performance in early clinical phases, no engineered therapeutic bacteria have yet received approval, primarily due to challenges in proving efficacy while ensuring biosafety. Material science innovations, particularly the encapsulation of bacteria within hydrogels, present a promising avenue to enhance bacterial survival, efficacy, and safety in therapeutic applications. This review discusses this interdisciplinary approach to develop living therapeutic materials. Hydrogels not only safeguard the bacteria from harsh physiological conditions but also enable controlled therapeutic release and prevent unintended bacterial dissemination. The strategic use of encapsulation materials could redefine the delivery and functionality of engineered bacterial therapeutics, facilitating their clinical translation.
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 combined 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.
Silver nanowires (AgNW) find use in transparent conductive electrodes with applications in solar cells, touch screens, and wearables. Unprotected AgNW are prone to atmospheric corrosion and lose conductivity over time. Known passivation techniques either require submersion of pre-deposited AgNW in liquid compounds or the modification of AgNW inks prior to deposition, which alters viscosity and complicates deposition. Here, new possibilities for stabilization of pre-deposited AgNW networks without need for submersion are explored. It is demonstrated that AgNW networks can be stabilized either by argon or hydrogen plasma treatment or by solvent vapor annealing with ethanol, methanol, or ethyl acetate. These treatments yielded stable electrical resistance over at least nine weeks, whereas untreated or thermally annealed AgNW layers quickly lost conductivity. The potential of solvent vapor annealing is further explored by demonstrating a new processing technique for stable polymer matrix composites containing AgNW. Co-deposited layers of AgNW with polystyrene microbeads are annealed in ethyl acetate vapor to stabilize the AgNW while at the same time merging polymer beads into a closed film around the AgNW. The resulting composites maintained stable resistance and transmittance for at least seven weeks.
Nature achieves diverse biological functions through structure formation. Inspired by the controlled formation of polypeptide nanostructures in cells, synthetic methods have been developed to assemble artificial nanostructures and organelle-like compartments within living cells. While these synthetic intracellular assemblies have mostly been used to disrupt cellular processes, their potential to induce a gain of function within cells remains unexplored. Here, we introduce redox-sensitive isopeptides that transform into self-assembling linear peptides inside human cytotoxic T cells in response to intracellular levels of glutathione. The in situ formation of synthetic peptide nanostructures in cytotoxic T cells leads to cellular stiffening, establishing a direct interface between biochemically driven peptide assembly and mechanobiological effects. This change in biophysical properties, along with increased phosphorylation of signaling proteins associated with T cell activation, correlates with a significant enhancement in the efficacy of cytotoxic T cells to eliminate cancer cells. Our findings elucidate the cellular impact of synthetic peptide nanostructures assembled within living cytotoxic T cells and demonstrate their ability to modulate and enhance effector immune cell responses.
Synthetic cells have emerged as novel biomimetic materials for studying fundamental cellular functions and enabling new therapeutic approaches. However, replicating the structure and function of complete tissues as self-organized 3D collectives has remained challenging. Here, we engineer lymph node-mimicking 3D lymphatic bottom-up tissues (lymphBUTs) with mechanical adaptability, metabolic activity, and hierarchical microstructural organization based on individual synthetic cells. We demonstrate that primary human immune cells spontaneously infiltrate and functionally integrate into these synthetic lymph nodes to form living tissue hybrids. By tuning the lymphBUT micro-organization and metabolic activity, we induce the ex vivo expansion of therapeutic CD8+ T cells with an IL-10+/IL-17+ regulatory phenotype. Our study highlights the functional integration of living and non-living matter, advancing synthetic cell engineering toward 3D tissue structures.
Self-assembly, a fundamental property of living matter, drives the interconnected cellular organization of tissues. Synthetic cell models have been developed as bionic materials to mimic inherent cellular features such as self-assembly. Here, we leverage co-assembly of synthetic and natural cells to create hybrid living 3D cancer cultures. We screened synthetic cell models, including giant unilamellar vesicles, coacervates, microdroplet emulsions, proteinosomes, and colloidosomes, for their ability to form hybrid tumoroids. Our results identify the balance of inter- and extracellular adhesion and synthetic cell surface tension as key material properties driving successful co-assembly of hybrids. We further demonstrate that these synthetic cells can establish artificial tumor immune microenvironments (ART-TIMEs), mimicking immunogenic signals within tumoroids. Using the ART-TIME approach, we identify co-signaling mechanisms between PD-1 and CD2 as a driver in immune evasion of pancreatic ductal adenocarcinoma. Our findings demonstrate the 3D bottom-up self-assembly of hybrid cancer microenvironments to replace immune components with defined bionic materials, pushing the boundaries to functionally integrating living and non-living matter.