Over the last decade, Russia’s political regime has become increasingly anti-Western in its rhetoric and ideational foundations. At the same time, Russian social sciences, and particularly economics, have pursued the path of internationalization, declaring the goal of becoming part of the global academic community. How can one reconcile these two contradictory trends? The article offers an in-depth investigation of the evolution of the internationalization of economics in Russia since the fall of the Soviet Union. The authors argue that internationalization is a complex phenomenon, with some of its aspects being problematic for the anti-Western regime, with others being acceptable or even beneficial. In particular, they focus on the tension between two goals of internationalization: dissemination of Western ideas and concepts in the domestic community (i.e. the role of translators and public intellectuals) and participation in the international exchange of ideas (i.e. publication in English-language scholarly journals). In the 2010s, Putin’s regime promoted the second goal at the expense of the first, which was potentially more problematic from the point of view of the regime’s logic. The authors also highlight the importance of economics as source of policy advice, even for an anti-Western regime like Putin’s.

Halogenated specialized metabolites show high chemical diversity and exhibit a range of biological activities. A targeted screening of a cyanobacteria extract library for halogenated specialized metabolites using HPLC-HRMS combined with MassQL and Haloseeker indicated that several of the extracts contained halogenated compounds, among them an extract of Tolypothrix sp. PCC9009. This freshwater cyanobacterium has been known since the early 1980s for producing the chlorinated specialized metabolite cyanobacterin, containing a γ-lactone core structure with a hydroxy group that is essential for its herbicidal activity against cyanobacteria and green algae. Mass-spectrometry-based molecular networking was employed to explore the chemical space of natural cyanobacterin analogues. This analysis led to the identification of 15 previously unknown compounds structurally related to cyanobacterin, most of which are related to anhydrocyanobacterin, including a dimer formed by [2 + 2] photocycloaddition. Two further analogues, previously reported following heterologous expression of the cyanobacterin biosynthetic gene cluster in E. coli as the nonchlorinated precyanobacterin I and II, were now isolated from the natural cyanobacterin producer. Cytotoxicity assays of cyanobacterin, anhydrocyanobacterin and one further isolated analogue showed only modest activity of the compounds against HCT116 cells.

In Russia, positive attitudes toward a free market economy and competition are firmly associated with the “Western” intellectual imports the country experienced in the 1990s. Anti-Western intellectuals and politicians typically embrace an anti-market stance calling for an economy with greater level of governmental interventions. There is a highly prominent exception to this logic: Putin himself appears to have a positive attitude toward free markets—in particular, free and unconstrained competition. This attitude does not seem to have changed even after the full-scale invasion of Ukraine in 2022. This article reviews Putin‘s rhetoric with respect to markets, competition, and economic freedom and offers several explanations for it. In addition to the more conventional story of the “authoritarian capitalism” logic, it offers a further explanation: the reinterpretation of markets in line with a “Darwinian” point of view where markets are perceived not as spaces of freedom but as spaces of hierarchy and power.

The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu4][OsNCl4] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C6F5OH) in the presence of Ag2O to obtain the stable complexes [NBu4][Os(N)(O2C(CF3)2)2] (1), [NBu4][Os(N)(O2C2(CF3)4)2] (2), [NBu4][Os(N)(OC6F5)4] (3), and [NBu4][Os(N)(Cl)2(O2C(CF3)2)] (4) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four O-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes 1 and 4 extend the coordination chemistry of the otherwise underrepresented O2C(CF3)2 ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds 1, 2, and 3 are analyzed.

Twenty-seven pyridine N-oxides (PyNOs) are investigated to evaluate the gelation of their silver(I) trifluoroacetate (AgTFA) complexes across eight solvents. Gelation occurs selectively with PyNOs featuring electron-donating groups, while those with electron-withdrawing or mixed groups do not form gels. A combination of two different PyNOs, one with an electron-donating group and the second with an electron-withdrawing group, form a gel, suggesting that gel-forming PyNO-AgTFA can override the non-gelling tendency of PyNOs comprising electron-withdrawing groups. Pyridine-AgTFA complexes lacking the N–O group fail to gel, underscoring the crucial role of the N–O functionality and its coordination with silver(I) in facilitating gelation. The resulting PyNO-AgTFA gels demonstrate remarkable mechanical strengths, enabling the fabrication of free-standing and load-bearing gel shapes, such as rods and horseshoes, with sizes up to several centimeters. The analysis of 65 X-ray crystal structures reveals that PyNO-AgTFA complexes manifest four distinct structural motifs, even when crystallized under different solvents and ligand-to-metal ratios, demonstrating a strong preference for a specific set of silver(I) complexes. X-ray crystallography and powder X-ray diffraction studies predict gel structures without single crystals. Density functional theory calculations of recurring non-covalent interactions in the crystal structures show interaction energies ranging from −1 to −92 kJ mol−1.

In this article, we propose a series of latent trait models for the responses and the response times on low stakes tests where some test takers respond preliminary without making full effort to solve the items. The models consider individual differences in capability and persistence. Core of the models is a race between the solution process and a process of disengagement that interrupts the solution process. The different processes are modeled with the linear ballistic accumulator model. Within this general framework, we develop different model variants that differ in the number of accumulators and the way the response is generated when the solution process is interrupted. We distinguish no guessing, random guessing and informed guessing where the guessing probability depends on the status of the solution process. We conduct simulation studies on parameter recovery and on trait estimation. The simulation study suggests that parameter values and traits can be recovered well under certain conditions. Finally, we apply the model variants to empirical data.

The general historiography of Israel is still shaped by the assumption that Zionism was “anti-urban,” despite the country’s early de facto urbanization and comprehensive scholarship contradicting this claim. Addressing these tensions, this article revisits the Zionist intellectual and settlement history in the pre-state period. To many Zionists, I argue, the city symbolized Western-style modernization and development. Their attitudes toward it were, therefore, more ambivalent and indeed synthetic: “Rurban” settlement designs provided a compromise between Euro-modernity and a “return to the East.” In this light, the Yishuv/Israel’s eventual “turn to the city” must also be understood in the context of a growing commitment to European civilization.

Chiral plasmonic nanostructures enable exceptionally high dissymmetry factors (g-factors) compared to chiral molecules and present unparalleled opportunities in light manipulation, polarization-sensitive photochemistry, and chiral sensing. Here polarization-dependent plasmonic chemistry on chiral gold nanocubes (AuNCs) is presented, leveraging the high sensitivity of surface-enhanced Raman scattering (SERS). The AuNCs exhibit strong optical activity and localized surface plasmon resonances acting as highly efficient nanoscale light antennae. Employing the hot electron-induced dehalogenation of 8-Bromoadenine as a model reaction, it is demonstrated that circularly polarized light induces asymmetric reaction rates due to circular dichroism (CD) in hot electron generation efficiency. Astonishingly, the photochemical g-factor, quantified by the differential reaction rate coefficients under left-handed and right-handed circularly polarized light, surpasses its optical counterpart and can be further enhanced by laser intensity. Remarkably, multilayer assemblies of AuNCs exhibit a reversal in photochemical CD, which is tuneable via laser power and enables further g-factor enhancement. Comprehensive electromagnetic simulations of extinction spectra and hot electron generation maps corroborate the profound impact of particle arrangement on the optical g-factor and the g-factor for hot-electron generation. This work demonstrates a systematic approach to enhance the photochemical chiroptical response of chiral AuNCs, paving the way for extraordinary control over chemical reactions with light.

Herein, [NEt3Me]2[PdCl4] is reported as a highly active catalyst for the mercury-free hydrochlorination of acetylene to vinyl chloride, resulting from the combination of the bichloride-based ionic liquid [NEt3Me][Cl(HCl)n] with PdCl2. Replacing gaseous HCl with the bichloride shifts the reaction in the liquid phase increasing the process safety by pressure reduction and achieves a turnover frequency of TOF = 110 molVCM h−1 molPdCl2−1 matching the productivity of state-of-the-art heterogeneous systems. Additionally, [NEt3Me]2[PdCl4] shows remarkable long-term stability and can be re-used over ten reaction cycles (200 h in total) without any problems due to its resistance to reduction by acetylene and coking as revealed by kinetic, theoretical, and spectroscopic investigations. Finally, initial catalytic studies demonstrate promising outcomes for applications of the bichloride-based ionic liquids with other noble metals, like platinum, if disproportionation phenomena, as observed for gold, do not occur.

Speech prosody is essential for conveying communicative intentions. Although neurophysiological data has shown that communicative functions conveyed through prosody are processed rapidly in the human brain, it is still unclear when and to what extent prosodic information is needed for the conscious speech act recognition as speech unfolds. Using a gating paradigm, we investigated the point at which listeners recognise the function of identical Italian sentences – whether they express a question or statement – based on vocal intonation. Comparing cross-spliced and natural sentences, we found that, rising or falling nuclear accentual movement on the sentence-final word seems to be the primary cue for recognition, with questions identified slightly later than statements. Furthermore, we discuss the limitations of splicing techniques in filtering out natural prosodic variations, the presence of a “statement bias” in perceiving incomplete sentences, along with a visual examination of interindividual responses. These findings offer valuable insights into the timing of conscious recognition of different communicative functions based on speech prosody.

Current attempts to transform our fossil fuel-based society into a sustainable one involve learning from and employing the biochemistry of nature. The process of photosynthesis is exemplary for utilizing sunlight as a regenerative energy source. Enzymes like hydrogenases, which reduce protons to molecular hydrogen (H2) under ambient conditions, are model biocatalysts for generating sustainable, clean fuels. In green algae, photosynthesis and hydrogenases are coupled through ferredoxin, a small electron transfer protein. Here, it is shown that several plant-type ferredoxins can interact with a chemically synthesized active site cofactor analog of [FeFe]-hydrogenases in a way that allows comparably high H2 evolution rates. UV–vis and Fourier-transform infrared spectroscopy indicate that the natural [2Fe-2S] clusters of the ferredoxin hosts must be absent for a functional interaction of polypeptide and cofactor mimic and that the apo-ferredoxins shield the H2-producing cofactor from the solvent. The hybrid proteins exhibited higher O2 tolerance than natural [FeFe]-hydrogenases and generated H2 in light-dependent cascades based on photosystem I or the chemical photosensitizer proflavine. These features and the combination of natural hosts and cofactors might contribute to establishing sustainable light-dependent H2 production systems.

This article aims to contribute to the literature about the roles and limitations of alternative media activism in different hybrid media systems by scrutinizing the organizational and discursive counter-hegemonic agency of digital alternative platforms in the Lebanese media system that is prone to high political parallelism, elite control, and polarization. To achieve this objective, semi-structured interviews with Lebanese journalists and a qualitative framing analysis for the alternative and mainstream media coverage of the Beirut Port explosion, which took place on the 4 August 2020 and led to the death of hundreds of people, were conducted. Our results show that Lebanese alternative media strive to escape the hegemonic control of sectarian and political groups by trying to achieve editorial and financial independence. Besides, they attempted in their framing of the explosion to develop a different narrative of the political conflict as a meta-sectarian one between the people and the ruling class from all the sects. However, they face the challenge of distinguishing themselves from the mainstream oppositional media that stands against the current regime. These results highlight the challenges and new possibilities opened by digital technologies for alternative media to escape the political hegemony in a polarized hybrid media system.

3D nanosystems equipped with polysulfates as binding sites are effective virus inhibitors due to their ability to dynamically deform while adhering to a virus. Here, a new supramolecular nanosystem assembled from a block copolymer consisting of sulfated linear polyglycerol and polytrimethylene carbonate is presented. It exhibits a unique morphology, 100 nm sized spheres with a distinct brush-like corona. The negatively charged sulfates are distributed on the outer shell and enable exceptional homogeneity of the particles, thereby enhancing the efficiency of multivalent interactions. Various sulfation levels are tested and demonstrated extremely low half-maximal inhibition concentration (IC50) values in plaque reduction assays tested on herpes simplex virus type-1 (HSV-1): 0.43, 0.16, and 0.037 µg mL−1 of the 45%, 76% and 100% sulfated assemblies, respectively. Using cryo electron microscopy (cryo-EM), viruses trapped are observed by multiple layers of the nano-assemblies. Both 76% and 100% sulfated assemblies show therapeutic potential in the post-infection model. The inhibitory behavior of the 76% and 100% sulfated assemblies is further confirmed against Omicron infection. This work demonstrates that the presented 3D flexible nano-assemblies can block the virus entry into the host cells with superior morphology and efficiency, establishing them as a promising candidate for antiviral applications.

We report on the first push-pull quino [3]radialene fluorescent dye. Here, the novel bis(dicyanomethylene)-[3]radialene electron acceptor was connected to a benzimidazole donor. With protonation a substantial red-shift of fluorescence wavelength is observed, while the absorption maximum remains stable. This process is accompanied with an increased fluorescence quantum yield to about 70%. Further, we explain the findings by a combined experimental and theoretical approach and find that vibronic coupling plays a crucial role. This study highlights the yet unexplored potential of [3]radialene-based motifs for the design of environment-responsive fluorophores.

The development of immunocompetent skin models represents a significant advancement in in vitro methods for detecting skin sensitizers, adhering to the 3R principles aimed at reducing, refining and replacing animal testing. In the present study, an advanced skin model from hair follicle-derived cells was constructed and enriched with two key immune cell types, namely Langerhans cells and T-lymphocytes, named ImmuSkin-MT. The model features a physiologically relevant epidermis and dermis, integration of monocyte-derived Langerhans cells (MoLCs) beneath the dermal layer, and co-cultivation with CD4+-T cells in the lower chamber of a transwell system. This setup closely mimics the native interplay between skin-resident immune cells and T-cells, marking a significant advancement in in vitro toxicology. When exposed to known sensitizers of varying potency, the model demonstrated a robust ability to predict the sensitizing potential of chemicals. By addressing different key events in skin sensitization, a differentiation between extreme, moderate and even weak sensitizers was achieved. The results showed that the MoLCs migrated, and upregulated CD86 expression in response to contact sensitizers. Additionally, proliferation of CD4+ T-lymphocytes was increased in response to the treatment. These results highlight the potential of the ImmuSkin-MT construct to serve as a valuable tool for mechanistic studies and future regulatory applications in the assessment of skin sensitization.

Most faunas from the Mesozoic era were dominated by sauropod dinosaurs, the largest terrestrial animals to ever exist. These megaherbivores were remarkably diverse and widely distributed. Here we study three Late Jurassic faunas from the USA, Portugal and Tanzania, each approximately 150 million years old, which are known for their extreme sauropod diversity. Whereas general taxonomic composition was similar in these three faunas, the major clades differed in relative abundance. Moreover, their depositional strata record distinct climatic regimes. Using dental microwear texture analysis, we investigated the impact of these climate regimes and the resulting food availability on the different sauropod taxa. Wear patterns in camarasaurid macronarians show minimal variation across different climate regimes, supporting previous studies suggesting that these animals migrated to follow their preferred climate niche and food source. North American camarasaurids show similar wear patterns to those of Portuguese turiasaurs, another broad-crowned taxon, which did not exist in the Jurassic of North America. By contrast, where camarasaurids and turiasaurs co-occurred in Portugal, their microwear patterns are distinct, suggesting niche differentiation to avoid ecological competition between these two clades. Flagellicaudatan diplodocoids display highly variable wear patterns, indicating limited migration (and therefore seasonal variation in diet), which aligns with observed biogeography patterns in the USA. Early-branching titanosauriforms show highly distinct wear patterns between different climate regimes, which can probably be attributed to different abrasive loads in the respective habitats. Our results demonstrate that dental microwear texture analysis not only records dietary preferences but also reveals behaviour such as competition and migration related to dietary niches in past ecosystems.

An 8-year-old, 1.06 kg, male castrated, domestic ferret (Mustela putorius furo), was presented with an antifreeze (ethylene glycol) poisoning. The relevant medical history shows a T-cell lymphoma diagnosed 8 months ago and was being treated with prednisolone. At the initial examination, an ataxic gait was noted and blood, urine and abdominal ultrasound tests were performed during the 48-h hospitalisation. During hospitalisation, clinical examinations revealed ataxia, apathy, somnolence, hypothermia, salivation, vomiting, anorexia and anuria. Blood tests and ultrasound examinations revealed the development of azotemia with reduced urine-specific gravity and loss of renal structure, with renal medulla and cortex no longer being differentiated. Treatment included ethanol infusion, metoclopramide, maropitant and furosemide. The ferret died of acute renal failure 48 h after initiation of therapy and autopsy confirmed antifreeze intoxication as the cause of death. Antifreeze poisoning in ferrets is underreported but possible. Prognosis is poor without immediate therapy.

Homozygous sauteur d'Alfort rabbits have a splicing-site mutation in the RAR-related orphan receptor B (RORB) gene that causes changes in their locomotion. These rabbits sometimes walk on their thoracic limbs, especially at higher speeds. They also experience additional abnormalities, including eye alterations such as blindness due to retinal dysplasia, cataract formation, lens luxation, coloboma, glaucoma and other complications. This report describes two 17-month-old intact female dwarf rabbits that have exhibited locomotory disturbances since their first few weeks of life and severe eye alterations since they were several months old. Both animals appeared smaller than their other siblings. The locomotory and eye alterations resemble those observed in sauteur d'Alfort rabbits. Genetic analysis showed that both rabbits were homozygous for the wild-type mutation in the RORB gene. This indicates that their behavioural and ocular alterations were attributable to a distinct genetic basis rather than the sauteur d'Alfort allele.

What explains institutional change in global financial regulation? We propose a model in which institutional change in response to exogenous shocks such as financial crises and legitimacy concerns is moderated by an endogenous variable, institutionalisation. We test our model using a mixed methods design. Relying on a newly constructed quantitative indicator of institutionalisation, we analyse 16 global regulatory institutions from 1967 to 2017. We examine causal mechanisms in three case studies using a new distinction between informal, contract- and treaty-based institutions. Our results support the model. Lowly institutionalised and informal institutions, like the Basel Committee on Banking Supervision, experienced significant institutional change and formalisation, becoming contract-based institutions. Contract-based institutions with intermediate institutionalisation, such as the International Accounting Standards Board, underwent change but remained in their category. Treaty-based institutions with high institutionalisation, like the International Monetary Fund, largely resisted change. These findings address gaps and complement the literature on global finance by providing a systematic large-N analysis with a focus on institutional development. We also contribute to historical institutionalism by highlighting the interaction of exogenous and endogenous factors, and to the literature on institutional choice between formal and informal IOs.

The highly reactive ozonide anion could be stabilized for the first time with a ferrocene-based cation resulting in the title compound [CpFeCpCH2NMe3]O3·1.47 NH3. The target compound was thoroughly characterized by X-ray diffraction [P21/c a = 1778.33(8) pm, b = 811.70(4) pm, c = 1111.71(5) pm, β = 91.715(2)°, R = 0.0325, 40301 reflections]. Additionally, infrared spectroscopy as well as quantum chemical calculations of the embedded anion were carried out to further characterize the compound and investigated the O-O bond lengths and O-O-O bond angles of the ozonide anion.