Publikationen

Fingertip friction is a key component of tactile perception. In active tactile exploration, friction forces depend on the applied normal force and on the sliding speed chosen. We have investigated whether humans perceive the speed dependence of friction for textured surfaces of materials, which show either increase or decrease of the friction coefficient with speed. Participants perceived the decrease or increase when the relative difference in friction coefficient between fast and slow sliding speed was more than 20 %. The fraction of comparison judgments which were in agreement with the measured difference in friction coefficient did not depend on variations in the applied normal force. The results indicate a perceptual constancy for fingertip friction with respect to self-generated variations of sliding speed and applied normal force.

Lithium-ion batteries (LIBs) are at the forefront of technological innovation in the current global energy-transition paradigm, driving surging demand for electric vehicles and renewable energy-storage solutions. Despite their widespread use and superior energy densities, the environmental footprint and resource scarcity associated with LIBs necessitate sustainable recycling strategies. This comprehensive review critically examines the existing landscape of battery recycling methodologies, including pyrometallurgical, hydrometallurgical, and direct recycling techniques, along with emerging approaches such as bioleaching and electrochemical separation. Our analysis not only underscores the environmental and efficiency challenges posed by conventional recycling methods but also highlights the promising potential of electrochemical techniques for enhancing selectivity, reducing energy consumption, and mitigating secondary waste production. By delving into recent advancements and juxtaposing various recycling methodologies, we pinpoint electrochemical recycling as a pivotal technology for efficiently recovering valuable metals, such as Li, Ni, Co, and Mn, from spent LIBs in an environmentally benign manner. Our discussion extends to the scalability, economic viability, and future directions of electrochemical recycling, and advocates for their integration into global battery-recycling infrastructure to address the dual challenges of resource depletion and environmental sustainability.

Cofactor regeneration systems are of major importance for the applicability of oxidoreductases in biocatalysis. Previously, geranylgeranyl reductases have been investigated for the enzymatic reduction of isolated C=C bonds. However, an enzymatic cofactor-regeneration system for in vitro use is lacking. In this work, we report a ferredoxin from the archaea Archaeoglobus fulgidus that regenerates the flavin of the corresponding geranylgeranyl reductase. The proteins were heterologously produced, and the regeneration was coupled to a ferredoxin reductase from Escherichia coli and a glucose dehydrogenase from Bacillus subtilis, thereby enabling the reduction of isolated C=C bonds by purified enzymes. The system was applied in crude, cell-free extracts and gave conversions comparable to those of a previous method using sodium dithionite for cofactor regeneration. Hence, an enzymatic approach to the reduction of isolated C=C bonds can be coupled with common systems for the regeneration of nicotinamide cofactors, thereby opening new perspectives for the application of geranylgeranyl reductases in biocatalysis.

Abstract Extracellular vesicles (EVs), through their complex cargo, can reflect the state of their cell of origin and change the functions and phenotypes of other cells. These features indicate strong biomarker and therapeutic potential and have generated broad interest, as evidenced by the steady year-on-year increase in the numbers of scientific publications about EVs. Important advances have been made in EV metrology and in understanding and applying EV biology. However, hurdles remain to realising the potential of EVs in domains ranging from basic biology to clinical applications due to challenges in EV nomenclature, separation from non-vesicular extracellular particles, characterisation and functional studies. To address the challenges and opportunities in this rapidly evolving field, the International Society for Extracellular Vesicles (ISEV) updates its ‘Minimal Information for Studies of Extracellular Vesicles’, which was first published in 2014 and then in 2018 as MISEV2014 and MISEV2018, respectively. The goal of the current document, MISEV2023, is to provide researchers with an updated snapshot of available approaches and their advantages and limitations for production, separation and characterisation of EVs from multiple sources, including cell culture, body fluids and solid tissues. In addition to presenting the latest state of the art in basic principles of EV research, this document also covers advanced techniques and approaches that are currently expanding the boundaries of the field. MISEV2023 also includes new sections on EV release and uptake and a brief discussion of in vivo approaches to study EVs. Compiling feedback from ISEV expert task forces and more than 1000 researchers, this document conveys the current state of EV research to facilitate robust scientific discoveries and move the field forward even more rapidly.

A special issue highlighting contributions of women to Chemical Research in Toxicology. The United Nations sustainable development goals aim to improve health and education and promote economic growth while reducing inequality and ending poverty. The field of toxicology is intrinsically dedicated to these goals, addressing the protection of the world population through improving public health and ensuring access to clean water and the sustainable consumption and production of safe food. Specifically, the identification and quantification of hazards and exposures, the chemical and molecular understanding of associated biological outcomes, and tools and models for the prediction of adverse outcomes form a solid basis for hazard reduction, substitution, or safe and sustainable design. In this context, the necessity for the full inclusion of women in all areas of sustainable development has been elevated by the United Nations by making the empowerment of all women and girls one of its sustainable development goals. (1) To fully reach this goal, this empowerment must include the eradication of the gender gap in research and experimental development in science. According to the UNESCO Institute for Statistics (UIS), in 2016, only 29.3% of employees in R&D worldwide were women. A closer look reveals that regional averages for the share of female researchers are heterogeneous, ranging from 48% for Central Asia and 33% for North America and Western Europe to 19% for South and West Asia. (2) Furthermore, the representation of women seems to be inverse to academic rank or leadership position. (3) Although in some regions, e.g., in Europe, the absolute number of women employed as scientists and engineers grew over ten years by almost 50% to 7.3 million in 2022, this growth represented only a 2% increase in the proportion of women compared to men. (4) Shares of female researchers in the field of toxicology are less well accessible, but it can be assumed that overall women are underrepresented in this field, similar to other sectors. Based on the great success of the virtual issue of Chemical Research in Toxicology in Celebration of the International Day of Women and Girls in Science published earlier this year, (5) it is our pleasure to invite you to contribute to the planned special issue of Chemical Research in Toxicology, devoted to the promotion of the visibility of women in this field through the dissemination of their research. The CRT special issue “Women in Chemical Toxicology” is being Guest Edited by Prof. Dean Naisbitt and Prof. Sayuri Miyamoto, and CRT Associate Editor Dr. Annette Kraegeloh. This special issue is aimed at promoting the participation and accomplishments of women in the field of chemical toxicology. Therefore, we specifically call for submissions by first or corresponding authors at any stage in their career who identify as women. We welcome your submissions of research Articles, Rapid Reports, Perspectives, Reviews, or ToxWatch manuscripts related to the entire scope of Chemical Research in Toxicology. Authors are invited to send a presubmission inquiry to the Editors that includes an abstract and cover letter indicating the intended manuscript format by e-mail (eic@crt.acs.org). The deadline for submission is Monday, January 15, 2024. We look forward to your contributions!

Hybrid materials of core–shell particles and cellulose nanowhiskers (CNWs) were synthesized to produce opal films with increasing tensile strength. After the incorporation of CNWs into the processed particle films, differences in the mechanical and optical properties were noticeable, which stemmed from the adhesion forces between the cellulose and the particles’ shell material. Two different particle compositions were compared, using polystyrene as cores, and either poly(ethyl acrylate) (PEA) or a copolymer of ethyl acrylate and 3 wt % of 2-hydroxyethyl methacrylate (HEMA) as the shell material. Stronger interactions between the particles containing HEMA and the CNWs were displayed via atomic force microscopy particle manipulation experiments, where higher forces were required to deliberately move P(EA-co-HEMA) particles on a CNW substrate compared to PEA particles. The stronger interaction behaviors increased the disorder of the particles within the opal films toward photonic glasses with angle-independent structural colors. Also, the increase in tensile strength from <1 MPa at a cellulose content of 0 wt % to 6 MPa at the optimal CNW content of 15 wt % was more pronounced compared to the particle-cellulose mixture with only PEA in the particle shell. Thus, the presence of the hydroxy groups in the particles’ shell material on the molecular level significantly influenced the optical and mechanical properties on the macroscopic level.

Uric acid (UA) is one of the most electroactive low molecular weight compounds that can be electrochemically oxidized on the surfaces of numerous noble and non-noble electrocatalysts under applied polarization. Consequently, enzymatic determination of UA in model and real samples is complicated by possible interference between electrochemical and biochemical routes. Herein, a novel strategy for amperometric enzymatic hydrogen peroxide independent UA sensing at low concentrations (e.g., below 50 µM) is proposed. The UA-sensitive strategy relies on the use of screen printed electrodes modified by an electrodeposited hybrid functional sensing film comprising a non-noble electrocatalyst, a bioorganic layer containing enzyme uricase (UOx), and data acquisition enabling the biochemical transformation of UA to be distinguished from the electrochemical oxidation route. Performed selectivity test utilizing adenine, xanthine, urea, ascorbic acid, ethanol and glycerol did not reveal interferences during detection of UA. This proposed approach was tested for UA detection in model and fermentation samples. The quantitative results obtained in fermentation samples were validated through optical oxygen mini sensor studies and fluorescence-based bioassays.

Nine different derivatives of piperidino alanes of the general formula (CH2)5N-AlXY [X=Y=Cl (1), Br (2), I (3); X=(CH2)5N, Y=Cl (4), Br (5), I (6); X=H, Y=Cl (7), Br (8), I (9)] have been synthesized and compared with respect to their structures. All molecules form dimers with an Al2N2 central cycle and aluminum and nitrogen atoms in distorted tetrahedral environments as determined from X-ray diffraction. The three dihalide derivatives 1, 2 and 3 have C2h (2/m) symmetries in solution of which they maintain the Centro symmetry in the crystal lattice. The bis(piperidino) derivatives 4, 5 and 6 have either C1 (1) symmetry with the bridging piperidino cycles oriented in the same direction (4, 5) or Ci (ī) point symmetry as found for 6 (in solution at least one other isomer is present). Whereas the chlorine derivative 7 has crystallographic Ci (ī) symmetry, the bromine 8 has almost C2 and the iodine 9 crystallographic C2 (2) point symmetry. In solution all derivatives 7, 8, 9 show equilibria between cis (C2) and trans (Ci) isomeric forms (27Al NMR). The longest Al−N bond lengths within the rings are found for 5 (1.969(4) Å) and the shortest for 8 (1.940(4) Å). The ratio of Al⋅⋅⋅Al to N⋅⋅⋅N non-bonding distances in the almost square rings vary with the bulkiness of the terminal ligands at aluminum.

PeCa is a rare entity with rising incidence rates due to increased infections with human papillomaviruses (HPV). The distinct subtypes of PeCa with an individual pathogenesis demand biomarkers for a precise patient risk assessment regarding disease progression and therapeutic susceptibility. We recently identified promising candidates associated with an HPV-instructed tumor microenvironment (TME) using HPV-positive PeCa cell lines and tissue microarrays (TMA). The capacity of HPV + p63 + PeCa cells to release neutrophil-attracting CXCL-8 provided a molecular link explaining the infiltration of CD15 + myeloid cells in PeCa specimens. The candidate biomarkers HPV, p63, CD15, DKK1, and CD147 linked a tumor-promoting TME with a higher TNM classification reflecting more aggressive and metastasizing cancers. Based on immune-reactive scores (IRS) from TMA staining for these biomarkers, we calculated correlations and conducted association analyses to assess the degree of relationship between all biomarkers. We then conducted Kaplan–Meier survival estimates and Cox regression analyses to delineate the impact on PeCa patient survival. There is a notable predictive potential regarding the survival of patients with biomarker profiles beyond the potency of the individual biomarker. From all candidate biomarkers and biomarker profiles, the combination of CD147 and infiltrating CD15 + cells linked to an active HPV-driven transformation displayed cancer-immune dynamics with dismal prognosis for patients. After deciphering relevant interdependencies, the HPV + CD147 + CD15 + status was the most potent profile predicting metastasis-free survival of PeCa patients. The results of this report underscore the need for analysis of the TME and the development of multi-parameter composite scores that reflect fundamental cancer-immune relationships to tailor therapeutic interventions based on actual cancer immune dynamics.

Stinger-like structures in living organisms evolved convergently across taxa for both defensive and offensive purposes, with the main goal being penetration and damage. Our observations over a broad range of taxa and sizes, from microscopic radiolarians to narwhals, reveal a self-similar geometry of the stinger extremity: the diameter (d) increases along the distance from the tip (x) following a power law  , with the tapering exponent varying universally between 2 and 3. We demonstrate, through analytical and experimental mechanics involving three-dimensional (3D) printing, that this geometry optimizes the stinger’s performance; it represents a trade-off between the propensity to buckle, for n smaller than 2, and increased penetration force, for n greater than 3. Moreover, we find that this optimal tapering exponent does not depend on stinger size and aspect ratio (base diameter over length). We conclude that for Nature’s stingers, composed of biological materials with moduli ranging from hundreds of megapascals to ten gigapascals, the necessity for a power-law contour increases with sharpness to ensure sufficient stability for penetration of skin-like tissues. Our results offer a solution to the puzzle underlying this universal geometric trait of biological stingers and may provide a new strategy to design needle-like structures for engineering or medical applications.