The confinement of electromagnetic radiation to subwavelength scales relies on strong light–matter interactions. In the infrared and terahertz spectral ranges, phonon polaritons are commonly employed to achieve deeply subdiffractional light confinement, with such optical modes offering much lower losses in comparison to plasmon polaritons. Among these, hyperbolic phonon polaritons in anisotropic materials offer a promising platform for light confinement. Here we report on ultraconfined phonon polaritons in hafnium-based dichalcogenides with confinement factors exceeding λ0/250 in the terahertz spectral range. This extreme light compression within deeply subwavelength thin films is enabled by the large magnitude of the light–matter coupling strength in these compounds and the natural hyperbolicity of HfSe2. Our findings emphasize the role of light–matter coupling for polariton confinement, which for phonon polaritons in polar dielectrics is dictated by the transverse–longitudinal optical phonon energy splitting. Our results demonstrate transition-metal dichalcogenides as an enabling platform for terahertz nanophotonic applications.

Clustered O-glycosylation of long tandem repeat regions is the hallmark of secreted mucins such as MUC5AC. Glycosylation is thought to play a key role in rigidifying the peptide backbone. The synthesis of peptides containing extended O-glycosylation clusters has proven challenging, thus limiting studies on the influence of glycoclustering on peptide structure. Here, we report an efficient glyco-economic synthesis of peptides featuring a previously unattained degree of glycoclustering. The method is based on a fully automated, DMF-free solid-phase synthesis employing the solvent 1,3-dioxolane (DOL) in all steps. The addition of Tween-20 enabled fast couplings of and to GalNAcylated amino acids by using only 0.5 excess equivalents at room temperature. Five tandem repeats long MUC5AC glycopeptides containing up to 30 GalNAc residues (100% occupancy of potential glycosylation sites) were accessed by Diselenide–Selenoester Ligation and selective deselenization in the presence of terminal cysteine residues. Circular Dichroism (CD) measurements showed that progressive GalNAcylation shifts the conformational equilibrium from the random coil to the extended polyproline type II helix conformation. Pulsed Electron–Electron Double Resonance (PELDOR) spectroscopy measurements revealed a significant stiffening of the MUC5AC peptide backbone upon GalNAcylation of four or six amino acids in each octad repeat.

Livestock-associated methicillin-resistant Staphylococcus aureus (LA-MRSA) displays distinct geographical distribution patterns, with ST398 predominating in Europe and ST9 being the dominant lineage in Asia, particularly China. However, the mechanisms underlying these differences remain poorly understood. In this study, we evaluated the cell adhesion capacity, anti-phagocytic properties, and porcine nasal colonization potential of ST9 and ST398 strains isolated from China and Germany. Colonization dynamics and characteristics were further explored using 16S rRNA gene sequencing and metatranscriptomic analysis. Our findings revealed that LA-MRSA ST398 strains exhibited superior colonization capabilities, including enhanced cell adhesion, increased resistance to macrophage-mediated killing, and a stronger impact on nasal microbiota stability. Transcriptomic analyses during colonization indicated that ST398 strains prioritized pathways related to genome repair and amino acid metabolism, whereas ST9 strains, particularly those isolated from China, focused on carbohydrate metabolism. Although ST9 strains showed relatively weaker colonization capacity, the epidemic Chinese ST9 isolates carried multiple resistance genes [fexA, tet(L), and aadE-spw-lsa(E)-lnu(B)], exhibiting broad resistance to clinically important antibiotics including tylosin, florfenicol, and tetracyclines. This suggests that their prevalence in China may be maintained through antimicrobial selection pressure. With the implementation of stricter antibiotic use regulations in Chinese livestock production, ST398, due to its robust colonization potential, is likely to replace ST9 as the dominant LA-MRSA clone gradually.

The Lewis acid tris(4-bromo-2,3,5,6-tetrafluorophenyl)borane B(C6F4Br)3 was synthesized via transmetalation from BBr3 and AgC6F4Br. The latter was prepared from 1,4-C6F4BrSiMe3 with AgF and crystallized as a toluene solvate [2(AgC6F4Br)4•7.46(toluene)]. The solid-state structure of free B(C6F4Br)3 and its Lewis base adducts with EtCN, H2O, and POEt3 was determined by single-crystal X-ray diffraction. DFT calculations show that B(C6F4Br)3 has approximately 1% higher fluoride and hydride ion affinities (FIA and HIA) than tris(pentafluorophenyl)borane B(C6F5)3. Similarly, the Gutmann-Beckett method indicates an increase in Lewis acidity of 2%, whereas IR spectroscopy of the CD3CN adducts reveals a slightly lower ṽ(CN) vibration for B(C6F4Br)3. The presence of bromine atoms is expected to facilitate structural analysis of Lewis acid-base adducts of B(C6F4Br)3 by single-crystal X-ray diffraction in the future.

Chimeric antigen receptor (CAR) T cell therapy has revolutionized the treatment of hematologic malignancies; however, durable remissions remain limited due to antigen-negative cancer relapse, where tumor cells downregulate or lose the targeted antigen to evade immune recognition. To address this challenge, we developed cysteine-engineered CAR (CysCAR) T cells that redirect T cells to target cancer cells based on extracellular redox imbalances and the altered thiol/disulfide ratios, a marker we identified on B cell lymphomas. Here, we show that CysCAR-T cells, engineered with different cysteine-modified antibody fragments, exhibit a potent and specific cytotoxicity in vitro across various B cell lymphoma (BCL) subtypes, even in antigen escape models. Moreover, by integrating cysteine engineering with clinically used anti-CD19 CAR-T cells, we enabled simultaneous targeting of CD19 and altered redox states on BCL, potentially reducing the risk of antigen escape. In a pilot in vivo study, these bifunctional CD19-CysCAR-T cells suppressed tumor growth and prolonged survival of BCL-bearing mice without inducing systemic toxicity. Given that aberrant exofacial redox states are a hallmark of multiple cancers, our findings suggest a promising strategy to enhance the efficacy of anti-CD19 CAR-T cell therapy, overcome antigen escape, and reduce tumor relapse in BCL, with potential applicability to other malignancies.

The miniaturization of ferroelectrics with lateral size reduction is crucial for technological advancement but requires an understanding of the fundamental behavior of ferroelectrics at the nanoscale. While much attention has been focused on vertical scaling of perovskite ferroelectrics with thickness reduction, lateral scaling remains less explored. In this study, ferroelectricity is investigated in 20 nm thick single-crystalline BaTiO3 nanodisks with a diameter ranging from ≈ 400 down to 100 nm. They are fabricated by Ne ion milling of a 20 nm BaTiO3 film epitaxially grown on SrTiO3-buffered silicon. The nanodisks are ferroelectric with a Curie temperature in the range 230–270 °C as determined by temperature-dependent piezoresponse force microscopy. In 100 nm-diameter nanodisks, the vertical polarization component adopts three distinct patterns in the pristine state, aligning with theoretical predictions. The most prevalent pattern features a uniformly up-oriented vertical component. The rotational invariance of these domain patterns in the plane suggests a combination of center-type and flux-closure domains. Additionally, the up polarization can be switched progressively to down polarization upon application of a pulsed bias of increasing time width. The control of the polarization in nanostructures and of their progressive switching is of particular interest for memory applications.

Harnessing the catalytic power of heme catalysts for advanced synthesis, particularly in environmentally benign aqueous media, remains a significant challenge due to hemin's poor solubility and the need for precise microenvironment control. Here, the study reports a tailored amphiphilic random-block copolymer, poly(histidine-random-styrene)-block-poly(N,N-dimethylacrylamide) (P(His-r-Sty)-b-PDMAA), designed as an “all-in-one” nanocarrier for efficient aqueous hemin catalysis. Synthesized via controlled RAFT polymerization, this copolymer self-assembles into stable nanomicelles featuring a hydrophobic core functionalized with histidine residues for specific axial coordination of hemin, and a hydrophilic shell ensuring aqueous compatibility. This precisely engineered architecture enables the highly efficient cyclopropanation of styrene with ethyl diazoacetate in water using only 0.3 mol% hemin loading, achieving yields up to 94.4% under ambient air. The catalytic system demonstrates robustness and sustainability, retaining over 90% activity after four cycles via a simple extraction-based recovery. Thus, the work showcases a powerful strategy integrating controlled polymer synthesis and bio-inspired ligand design to create highly active and recyclable catalysts for challenging transformations in water.

The study addresses triaminoalkenes derived from [3]ferrocenophane-type cyclic (alkyl)(amino)carbenes (fcCAACs) fc(CPh2-C-NR) (fc = 1,1 '-ferrocenylene) and N-heterocyclic carbenes (NHCs). Stable target compounds are obtained in good yields as crystalline solids by the combination of [fc(CPh2-CH=NMe)][BF4] with N,N '-dimethylimidazolin-2-ylidene and of [fc(CPh2-CH=N-p-C6H4-tBu)](OTf) with 1,3,4,5-tetramethylimidazolin-2-ylidene, respectively, followed by treatment of the resulting addition product with KN(SiMe3)2. Due to the presence of a triaminoethene unit and a ferrocene moiety, four redox states are expected for such fcCAAC-NHC heterodimers, viz., electroneutral, mono-, di-, and tricationic. An investigation of their redox behavior by electrochemical methods (cyclic voltammetry and differential pulse voltammetry) has revealed that these compounds undergo two consecutive one-electron oxidations, with the poor stability of the dicationic species in solution preventing an observation of the tricationic redox state. A density functional theory (DFT) study shows that the highest occupied molecular orbital (HOMO) is localized on the C=CN2 atom, which, in agreement with electron paramagnetic resonance results, is the site of the first oxidation. The second oxidation mainly involves the Fe atom, where the HOMO-1 is localized, resulting in a species with a triplet ground state composed, to a first approximation, of a carbon-centered and an iron-centered radical.

Medicinal plants play an important role as therapeutics. Graphite furnace atomic absorption spectrometry (GFAAS) is used to monitor their quality for essential element content and potential contamination with heavy metals. This review summarizes recent applications of GFAAS for the analysis of medicinal plants and some pharmaceutical preparations made thereof. Attention is paid to the analytical conditions, in particular the applied pyrolysis and atomization temperatures as well as the use of modifiers. A brief focus on the respective properties of the medicinal plants presented demonstrates that GFAAS is a versatile technique for pharmaceutical analysis.

Ziele

Internationale Studien deuten auf ungünstige Wechselwirkungen zwischen ungewollten Schwangerschaften und psychischer Gesundheit. Die Studie untersucht Prävalenz, Ausgang und soziale Faktoren ungewollter Schwangerschaften bei psychisch erkrankten Frauen in Deutschland.

Methodik

In einer Querschnittstudie wurden 4495 Frauen über das Melderegister sowie 478 Frauen über relevante Anlaufstellen rekrutiert und zu Anzahl, Gewolltheit, Schwangerschaftsausgang und sozialen Kontextbedingungen befragt.

Ergebnisse

Frauen mit psychischen Erkrankungen zeigen ein erhöhtes Risiko für ungewollte Schwangerschaften (OR=1,6), Abbrüche (OR=1,6) und ungewollt ausgetragene Schwangerschaften (OR=1,8). Ungewollte Schwangerschaften treten bei Frauen mit psychischen Erkrankungen häufiger in belastenden Lebensumständen auf.

Schlussfolgerung

Die Wechselwirkungen zwischen ungewollten Schwangerschaften, psychischer Gesundheit und sozialen Belastungen verdeutlichen die Notwendigkeit, Aspekte der reproduktiven Gesundheit in der Versorgung von Frauen mit psychischen Erkrankungen zu berücksichtigen.

Cyanobacteria blooms pose a substantial threat to freshwater systems globally. While zooplankton grazers such as Daphnia can have an important role in suppressing cyanobacteria blooms, cyanobacteria can adversely impact Daphnia fitness and even kill them. Earlier work has shown an evolutionary increase in tolerance to cyanobacteria across years and strong genotype × genotype interactions determining the interaction between Daphnia and the cyanobacterium Microcystis. Here, we test the hypothesis that Daphnia magna can adapt during 1 growing season to changes in dominant strains of Microcystis. Over 2 consecutive years, we collected D. magna clonal lineages and Microcystis strains from a single pond early and late in the growing season and we assessed whether Daphnia survival differed when exposed to Microcystis strains from either the same or a different time point within the growth season. Our findings reveal important Daphnia genotype × Microcystis genotype interactions, with Daphnia survival being higher when exposed to Microcystis from the same time point than when exposed to Microcystis of a different time point. Our results extend earlier findings to variation within 1 single natural system and growth season, and suggest an important impact of rapid (co)evolutionary dynamics shaping the tolerance of zooplankton grazers to cyanobacteria.

Tessellations of the Euclidean plane and a circle, a model of the hyperbolic plane, impress by their beauty, elegance and balance equally mathematical amateurs as mathematicians. Besides its impressive figures, esthetic and elegance of related basic formulas affect scientists. The parqueting-reflection method provides besides the tiling related fundamental solutions to complex partial differential equations in the domains of the tessellation.

This paper examines judges and judgement in Bavarian dispute charters from the first decades of the ninth century. It argues that justice in Carolingian Bavaria was an amateur affair, in which of primary importance was the ability to create a stable consensus around an outcome. Accordingly, distinctions between judges and other participants in judicial assemblies were blurred, and the capacities in which assembly-goers participated often blended into each other. Even when royal agents intervened in the region, they did this mainly through, rather than against, the consensus dynamics of local judicial assemblies.

Human vision is mediated by a complex interconnected network of cortical brain areas that jointly represent visual information. Although these areas are increasingly understood in isolation, their representational relationships remain unclear. Here we developed relational neural control and used it to investigate the representational relationships for univariate and multivariate functional magnetic resonance imaging (fMRI) responses of areas across the visual cortex. Through relational neural control, we generated and explored in silico fMRI responses for large numbers of images, discovering controlling images that align or disentangle responses across areas, thus indicating their shared or unique representational content. This revealed a typical network-level configuration of representational relationships in which shared or unique representational content varied on the basis of cortical distance, categorical selectivity and position within the visual hierarchy. Closing the empirical cycle, we validated the in silico discoveries on in vivo fMRI responses from independent participants. Together, this reveals how visual areas jointly represent the world as an interconnected network.

‘Business and Human Rights’ (BHR) has congealed as the predominant framework to conceive and address violence in the context of transnational production networks. This article presents an analysis of the assumptions regarding the nature of violence, its underlying economic causes and potential remedies that underpin contemporary BHR regulations. Drawing from literature on primitive accumulation and taking the German ‘Supply Chain Due Diligence Act’ as an example, the text argues that the Act distinguishes legal and illegal forms of doing business in a way that reproduces liberal accounts of capitalism’s relation to violence. In outlawing extreme forms of labour exploitation, environmental harm, illegal evictions and physical repression, the Act disconnects violent dispossession, repression, and over-exploitation from the normal, everyday workings of global capitalism. At the same time, it posits the normal functioning of capitalist accumulation as a non-violent alternative, thus failing to account for the violence of the market and the structural relation between capitalist and other forms of accumulation. Against this backdrop, the challenge for a critical BHR practice consists in using BHR norms to highlight instances of primitive accumulation, while simultaneously envisioning a future of work that does not seek redemption in ‘normal’ capitalist exploitation.

Connecting two-dimensional (2D) material layers via interface linkers represents a new avenue for fabricating 2D heterostructures. Utilizing light to remotely modulate this interface function allows for seamless assembly and patterning in a single run. Here, an efficient method for fabricating patterned 2D heterostructures using direct laser writing is demonstrated, drawing a conceptual parallel to laser printing. In the approach, functionalized transition metal dichalcogenide (TMD) dispersions serve as inks, graphene as the substrate, and a Raman laser as the patterning tool. Unlike laser printing's electrostatic interactions, the method achieves patterned assembly through covalent bonding between TMDs and graphene. Selective Raman laser irradiation of functionalized TMD/graphene heterostructures triggers localized reactions, forming chemically modified domains exclusively in the laser-irradiated regions, as confirmed by Raman spectroscopy, Kelvin probe force microscopy (KPFM), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Experimental and theoretical analyses of the interface composition and structure provide new insights into laser-induced chemistry. The work demonstrates the potential for high-throughput assembly of customizable 2D heterostructures, with enhanced compatibility for subsequent patterning through photolabile linkers and photoinduced coupling. Additionally, the results provide deeper insights into chemistry within confined 2D spaces, offering a novel approach to nanoscale heterostructure engineering.

This study examines the influence of mass obstruction tactics within the new climate movement on public support for activists and their goals. Using a survey experiment that manipulates different protest scenarios, we analyze the impact of obstructive protests with and without vigilante intervention on public opinion. Our results suggest that while obstructive tactics are perceived negatively by the public, they do not significantly affect support for climate activists’ goals. Vigilante repression does not moderate reactions to radical protests. The study highlights the complexity of using radical tactics in social movements and the challenges activists face in building coalitions and sustaining mobilization efforts.