Highly resolved vibrational spectra of the mononuclear Fe(II) spin-crossover complex [Fe(bpz)2(bipy)]; (bpz = dihydrobis(pyrazolyl)borate) and its dinuclear counterpart [{Fe(bpz)2}2μ–(ac(bipy)2)] (ac(bipy)2 = bridging ligand) are obtained by temperature-dependent far-infrared (FIR) spectroscopic measurements and assigned with the help of density functional theory (DFT) calculations. The experimental data confirm the high-spin (HS) state of the complexes at high temperature (≈ 200 K) and the low-spin (LS) state at 5 K. In the dimer, enhancement of otherwise absent vibrational modes at 335 cm–1 and 504 cm–1 around T1/2 reflects the presence of a mixed-spin HS-LS state during the course of the spin transition between HS-HS and LS-LS. The metastable HS state of the dinuclear complex resulting from light irradiation (532 nm) at 10 K results from a direct spin-state transition from LS-LS to HS-HS.

Ailios Aristeides saw himself as steeped in the tradition of Greek paideia, and his choice and representation of divinities largely reflect the same interest in classical ‘Greekness’ which pervades his works as a whole. One exception stands out: the ‘Egyptian’ gods Isis and, more prominently, Sarapis. The fact that Aristeides worships these gods is not in itself surprising, given their popularity in the second century CE. It does, however, raise the question of how Aristeides integrates them into a pantheon which he understands as rooted in a tradition without them. This article examines how Aristeides constructs and incorporates the ‘foreignness’ of Sarapis in the Hieroi Logoiand Hymn to Sarapisand what he gains from the god’s connection to Egypt. Aristeides, it is argued, balances Egyptian-connotated and Greek testimony to raise Sarapis to the status of a universal god and to make him comparable and compatible with a traditional picture of Greek divinity without assimilating him. Sarapis retains just enough Egyptian colouring to distinguish him from the other gods and lend Aristeides’ writings and religiosity a touch of ‘Egyptianness’. By assuming the compatibility of Egyptian and Greek religious traditions instead of either completely Hellenising or exoticising Sarapis, Aristides can draw on the authority of both to enhance, via Sarapis, his own claims to extra-institutional religious authority and exceptional nearness to the divine. His enterprise is facilitated by the importance of the written word as the basis of imperial Greek intellectual identity. Textuality gives Aristeides a way to bridge classical tradition with post-classical cultic reality: classical Greek texts supply him with a tradition of writing about Egypt into which he can fit the (for him) Egyptian god Sarapis, and the association of Egypt with expressly religious writings, with abundant ‘sacred texts’, both complements the very limited role of sacred texts in traditional Greek literature and religion and appeals to the value and authority which pepaideumenoiattach to the written word.

Integration against, and hence sampling from, high-dimensional probability distributions is of essential importance in many application areas and has been an active research area for decades. One approach that has drawn increasing attention in recent years has been the generation of samples from a target distribution Ptar using transport maps: if Ptar = T Pref is the pushforward of an easily-sampled probability distribution Pref under the transport map T , then the application of T to Prefdistributed samples yields Ptar-distributed samples. This paper proposes the application of transport maps not just to random samples, but also to quasi-Monte Carlo points, higher-order nets, and sparse grids so that the transformed samples inherit the original convergence rates that are often better than N−1/2, N being the number of samples/quadrature nodes. Our main result is the derivation of an explicit transport map for the case that Ptar is a mixture of simple distributions, e.g. a Gaussian mixture, in which case application of the transport map T requires the solution of an explicit ODE with closed-form right-hand side. Mixture distributions are of particular applicability and interest since many methods proceed by first approximating Ptar by a mixture and then sampling from that mixture (often using importance reweighting). Hence, this paper allows for the sampling step to provide a better convergence rate than N−1/2 for all such methods.

1. Global change and the loss of plant diversity threaten terrestrial ecosystem functionality. Microplastic pollution is considered a novel environmental stressor potentially affecting plant biomass production. However, it is poorly understood whether and how microplastic interacts with other global change factors, such as drought, to affect plant communities and the relationship between plant diversity and biomass production. 2. To unravel the above question and any underlying mechanisms, we conducted a glasshouse experiment. We assembled plant communities along a gradient of plant diversity and then subjected them to four microplastic and drought scenarios in grassland microcosms. 3. Our results showed that the positive effect of plant diversity on biomass production strongly depended on drought, whereas no significant interaction was found with microplastic, either alone or when combined with drought. Nevertheless, microplastic tended to decrease the positive diversity–biomass relationship by suppressing the shoot biomass of grasses and legumes, thereby reducing the positive selection effect. By contrast, drought significantly weakened this positive relationship by strongly reducing the shoot biomass of legumes, thereby inducing a negative complementarity effect and ultimately a negative net diversity effect. Both microplastic and drought decreased community biomass across all plant diversity levels, but microplastic could alleviate the negative effect of drought on community biomass by enhancing the shoot biomass of legumes. 4. Synthesis. Our findings reveal that microplastic and drought influence the positive effects of plant diversity on plant biomass production. Moreover, our study suggests that the mechanisms by which plant diversity affects productivity are differently sensitive to microplastic and drought. We highlight the importance of legumes in protecting and maintaining biodiversity and ecosystem functions in the face of microplastic pollution and drought risks.

Planning motor-actions involves the neuronal representation of key parameters such as force and timing prior to execution. Functional magnetic resonance imaging (fMRI) studies have shown that activity in premotor and parietal areas covaries with these parameters during motor-preparation. While previous research has demonstrated that parametric codes reflect graded grip-force intensities before and after their transformation into motor-codes, it remains unclear whether these representations are encoded in effector-specific brain-regions. To address this, we conducted an fMRI-study using a delayed grip-force task in which participants prepared one of four force-intensities with either their right or left cued-hand, with the hand to-be-used being switched in 50% of the trials midway through the delay. Using time-resolved multivoxel pattern analysis (MVPA) with a searchlight approach, we identified brain-regions encoding anticipated grip-force intensities of the cued-hand across the two 6-s delay-periods. In addition, cross-decoding analyses tested whether force-intensities were represented in an effector-specific or effector-independent format. We found above-chance decoding in two lateralized networks: the contralateral intraparietal sulcus (r−/l-IPS), as well as the lateral occipitotemporal cortex (r−/l-LOTC) during the first, and the contralateral primary motor cortices (r−/l-M1) during the second delay. These results indicate effector-specific coding of anticipated grip-force intensities, which is revealed by systematic lateralization of decoding-accuracy depending on the hand to-be-used. Cross-decoding corroborated effector-specific representation in these regions. Together, our results show that contralateral IPS and LOTCs encode effector-specific parametric information prior to M1s, likely reflecting a transformation process in which the intended grip-force intensity is selected, maintained, and then converted into detailed movement-plans.

Tetrahydromethyltestosterone (THMT) and 20-hydroxymethyl-18-nortetrahydromethyltestosterone (20OHnorTHMT) are metabolites of the anabolic androgenic steroids methyltestosterone and metandienone. Both molecular structures are used as markers in anti-doping analysis. There are eight reasonable diastereomeric structures of each group relevant for metabolic purposes. Highly sophisticated mass spectrometers fail to confidently differentiate these closely related, yet non-isomeric and non-isobaric groups of molecules. Due to the low abundance of the molecular ion, high-resolution mass spectrometry provides shared fragment ions that challenge identification by extracted ion chromatograms out of full scan mode acquisitions. Further on, tandem mass spectrometry uses partly the same ion transitions for both groups of targeted analytes. Thus, a reliable chromatographic separation is absolutely necessary. Therefore, a gas chromatographic method using a DB-5 ms capillary column (30 m, 0.25 mm, and 0.25 µm) was developed. Hence, discrimination between the two groups was enabled, and a confident structural assignment among the eight diastereomers was achieved. This case study contributes to a higher quality of anti-doping analysis, but even further raises awareness of the importance of chromatographic separation in cases of insufficient mass spectrometric discrimination.

In 2006, a unique collection of 73 Arabic diary volumes documenting thirty years of excavation (1913–1947) at fifteen archaeological sites in Egypt and Sudan resurfaced in the rural community of Quft (near Luxor) in the South of Egypt. They were written by two generations of archaeological foremen known as Quftis (after their town of origin) who worked with the Harvard University–Boston Museum of Fine Arts (HU–MFA) Egyptian Expedition. As was common to large-scale excavations in Egypt at the time, the expedition’s head foreman, Reis Sayyid Aḥmad Sayyid Dirāz (1890–1926), and several sub-foremen from Quft, were responsible for the day-to-day running of the excavations, including the recruitment and management of local labor. But in addition to employing Quftis as field technicians, who were skilled in excavation methods and the preservation of archaeological materials, the HU–MFA Expedition was unique in introducing Arabic record-keeping and site documentation. The resulting Arabic diary corpus is thus a one-of-a-kind archive in the history of archaeology – but it is also unique and equally important from the perspective of Arabic linguistics. The texts are written in a mixture of Classical (Standard) Arabic and Egyptian dialects, and they contain features reminiscent of Middle Arabic. This article discusses fragments of the first two diary books, written at Giza (near Cairo) and Deir el-Bersha (in Upper Egypt) between November 1913 and October 1915. Here we establish a preliminary basis for the diaries’ authorship; discuss the use of colloquial and Middle Arabic in the texts; and describe some features of linguistic and lexicographical interest.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and Middle East respiratory syndrome coronavirus (MERS-CoV) are two important targets in current drug discovery, mainly due to the COVID-19 pandemic and the MERS-CoV outbreaks in recent years. An important target of both SARS-CoV-2 and MERS-CoV is the main protease (Mpro). Recently, the ASAP Discovery Consortium focused on the acceleration of Mpro inhibitors with a part of this initiative being an open blind challenge in collaboration with Valence lab using the Polaris platform, where data sets of previously undisclosed inhibitors of SARS-CoV-2 Mpro and MERS-CoV Mpro were shared with researchers, to allow the development of machine learning and deep learning models for the prediction of the potency. We used this opportunity to evaluate and compare traditional machine learning models consisting of a random forest (RF) and gradient boosting model (XGBoost) with a bayesian neural network (BNN) model. For this purpose, we created single task models for the predictions of each of the targets. The results obtained showed that the BNN model outperformed both traditional machine learning models for both targets, indicating that BNNs are a promising deep learning framework in low-data regimes.

Fluorination of polymers is a powerful strategy to enhance chemical or material properties yet integrating these benefits into degradable polymers remains underexplored. Here, we report a new class of fluorinated polyesters synthesized via ring-opening copolymerisation of pentafluoro styrene oxide with phthalic anhydride. The pendant C6F5 groups accelerate catalysis through fluorine-specific π-stacking interactions and improve obtained molecular weights compared to the non-fluorinated variant giving access to high weight materials (Mn,max. > 100 kg mol−1) with thermal and mechanical properties competitive with commodity plastics. These C6F5 groups then act as reactive handles in the material for efficient post-polymerisation modification (PPM) in solution, allowing fine-tuning of thermal, mechanical, optical, and solubility properties. PPM can even be performed on material surfaces, films and fibres can be selectively modified without dissolution. Lastly, degradation enables quantitative recovery of fluorine centres as sodium fluoride, offering a sustainable end-of-life option for the incorporated fluorine. Our work demonstrates how targeted fluorination of degradable polyesters can simultaneously enhance catalysis and unlock advanced material functionality.

Climate change education and communications (CCE) has long been recognized as a critical vehiclefor increasing human and institutional capacity to mitigate against further climate change and to adapt to its impact. However, the global community lacks robust cross-national data and global indicators to measure and monitor progress in the planning, implementation, and delivery of CCE at the national and intergovernmental levels. This paper offers a synthesis of insights from interdisciplinary literature on indicator development conducted across the areas of education, education for sustainable development (ESD), communication and biodiversity and climate change. Bringing together independent histories of developing indicators for global benchmarking and target setting supports insights for the more nascent area at their intersections, that is, CCE. On the basis of the literature review, the orientation of ideal indicators could be synthesized as a guiding idea for indicator development. Ideal indicators have real-world congruence and are built on feasible data elicitation; they facilitate solutions for climate change and leverage political and public attention. In this article’s conclusion, we identify key challenges that can compromise indicators in the context of CCE (e.g., “smallest common denominator” -solutions) as well as possible countermeasures against these challenges.

A close reading of literary representations of automobility in Johannesburg in the late 2000s gives insight into the way in which freedom, mobility, and collective belonging are linked with the racialised and gendered discourse of modern, democratic citizenship. The literary representations mark automobility as a means to achieve progress in gender equality while remaining embedded in discourses that code positive representations of automobility as white. The lack of easy access to automobility for black women is linked to a perception of blackness as a marker of socio-economic exclusion and marginalisation, which impacts their identity formation and sense of belonging. The analysis engages with selected concepts from the field of mobility studies, namely Cresswell’s (2010) observation that mobility and modern citizenship are conceptually related, Bissell’s (2010) understanding of the formation of “mobile collectives,” and Sheller’s (2018) research into mobility justice. These will be used to analyse the role automobility plays in the emergence of a new black, female subjecthood in South African literature.

Cystitis is a frequent, often chronic and recurrent disease in guinea pigs (Cavia porcellus). This report describes a case of a 2-year-old, entire, female Abyssinian guinea pig with fatal cystitis. The animal was presented with progressive chronic cystitis and had previously been treated with several antibiotics and analgesics. Radiographs demonstrated a mineral-dense opacity in the urinary bladder, and urinalysis revealed numerous leukocytes. The animal received subcutaneous fluid boluses and a change of antibiotic treatment. The general condition deteriorated, and the animal died acutely 1 day after being admitted to the hospital. Pathology revealed severe, chronic-active, multifocal, purulent to fibrinous, haemorrhagic cystitis. A bacteriological examination of the urinary bladder wall and urinary bladder contents revealed Facklamia sourekii, Corynebacterium renale and Enterococcus casseliflavus. Myocarditis and steatitis were also noted, supporting sepsis secondary to cystitis as the cause of death.

Protein phosphorylation is one of the most important posttranslational modifications altering the structure, stability, and activity of more than 13 000 human proteins. In this work, the phosphotyrosine mimetic pentafluorophosphato-difluoromethyl-phenylalanine (PF5CF2Phe) was genetically encoded and incorporated into three different proteins. Screening two libraries of orthogonal aminoacyl-tRNA synthetases identified enzymes enabling the efficient and specific incorporation of PF5CF2Phe into red fluorescent protein (RFP) via amber stop codon suppression. Two model proteins, human ubiquitin (Ubq) and the B1 immunoglobulin-binding domain of streptococcal protein G (GB1), were prepared with PF5CF2Phe mutations and investigated for potential interaction partners. While native GB1 showed no binding to protein tyrosine phosphatases (PTP), PF5-GB1, with PF5CF2Phe at position 17, was a strong inhibitor of the phosphatases PTP1B and SHP2. PF5-Ubq was produced and converted into the first example of a protein carrying the most prominent phosphotyrosine mimetic, phosphono-difluoromethyl phenylalanine (PO3CF2Phe). With increasing need in the biosciences to delineate the functions of complex phosphorylation patterns, genetic encoding of PF5CF2Phe yielding phosphoprotein mimetics opens unique opportunities for precise functional studies where site-specific and homogeneous protein modifications are required.

Quantum measurements are probabilistic and, in general, provide only partial information about the underlying quantum state. Obtaining a full classical description of an unknown quantum state requires the analysis of several different measurements, a task known as quantum-state tomography. Here we analyse the ultimate achievable performance in the tomography of continuous-variable systems, such as bosonic and quantum optical systems. We prove that tomography of these systems is extremely inefficient in terms of time resources, much more so than tomography of finite-dimensional systems such as qubits. Not only does the minimum number of state copies needed for tomography scale exponentially with the number of modes, but, even for low-energy states, it also scales unfavourably with the trace-distance error between the original state and its estimated classical description. On a more positive note, we prove that the tomography of Gaussian states is efficient by establishing a bound on the trace-distance error made when approximating a Gaussian state from knowledge of the first and second moments within a specified error bound. Last, we demonstrate that the tomography of non-Gaussian states prepared through Gaussian unitaries and a few local non-Gaussian evolutions is efficient and experimentally feasible.

Self-assembly of lipid structures derived from amphiphilic molecules plays a crucial role in the development of biomimetic systems. Here we report a modular synthetic strategy for developing cholesteryl-oligo-glycerol-based surfactants with tunable head group functionalities ranging from nonionic to anionic. This approach enables the systematic incorporation of functional groups and thus precise control of surface charge and hydrophilicity. To investigate the influence of multivalent charges on supermolecular-assembly behavior, we compared three structurally cholesterol (CL) related surfactants: CL-4S, with four sulfate groups, CL-1S, with a single sulfate group, and CL-4OH, a nonionic analog with four hydroxyl groups. We then incorporated these surfactants into lipid bilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and cholesterol (CL) to study their behavior in membrane-like environments. Experimental, simulation, and theoretical studies demonstrated that the CL-4S formulation was able to convert lipid vesicles into nanodiscs, unlike CL-1S and CL-4OH, demonstrating the importance of adequate charges in supramolecular transition. Furthermore, both 1S-Vesicles (CL-1S based sulfated vesicles) and 4S-Nanodiscs (CL-4S based sulfated nanodiscs) showed inhibitory activity against herpes simplex virus-1 (HSV-1), indicating the potential of this multivalent supramolecular platform for antiviral applications.

The increasing prevalence of microbial resistance requires new antibacterial concepts for selective targeting and killing of pathogenic bacteria. Here, we report the synthesis of a heteromultivalent nanogel system against Pseudomonas aeruginosa (P. aeruginosa). These nanogels are based on biocompatible polyglycerols and functionalized with sugar ligands fucose (Fuc) or galactose (Gal) for P. aeruginosa targeting. With a further modification of these nanogels with BMAP-18 short chain peptides (GRFKRFRKKFKKLFKKLS), we have achieved > 99.99% inactivation of planktonic and > 99.9% inactivation of biofilm-coated P. aeruginosa within 12 h of treatment. Additionally, the system demonstrates broad-spectrum antimicrobial potential, effectively inhibiting Escherichia coli (E. coli) and Methicillin-resistant Staphylococcus aureus (MRSA). This modular design offers a promising strategy for the development of next-generation antimicrobial therapies targeting biofilm-associated infections and MDR bacteria.

Climate change increases the magnitude and frequency of extreme weather events. This includes severe summer storms altering lake physical structure, biodiversity and ecosystem processes. However, insights into lake responses to extreme storms and the underlying mechanisms primarily rest on unreplicated and observational case studies, without separating effects of physical forcing from secondary drivers such as external nutrient and dissolved organic matter inputs. In a large-scale replicated experiment conducted in a unique enclosure facility mimicking realistic environmental conditions, we tested how storm-induced mixing entails changes in lake ecosystems. Consequences include altered phytoplankton composition, nutrient, oxygen and carbon dynamics, with potential negative feedbacks on climate through organic matter sequestration. These experimental results are reflected in a minimal dynamical model and are also supported by observations made during a natural severe storm. An important practical implication is that efforts to abate lake eutrophication needs to accommodate the projected increases in extreme weather situations.

Many, but not all, parasitic filarial nematodes (Onchocercidae) carry intracellular, maternally transmitted, alphaproteobacterial Wolbachia symbionts. The association between filarial nematodes and Wolbachia is often portrayed as mutualist, where the nematode is reliant on Wolbachia for an essential but unknown service. Wolbachia are targets for antifilarial chemotherapeutic interventions for human disease. Wolbachia of Onchocercidae derive from four of the major supergroups (C, D, F, and J) defined within the genus. We explored the evolutionary history of the filarial nematode-Wolbachia symbiosis in 22 nematode species, 16 of which have current Wolbachia infections, by screening the nematode nuclear genome sequences for nuclear Wolbachia transfers, fragments of the Wolbachia genome that have been inserted into the nuclear genome. We identified Wolbachia insertions in 5 of the 6 species that have no current Wolbachia infection, showing they have previously had and have now lost Wolbachia infections. In currently infected species, we found a diversity of origins of the insertions, including many cases where they derived from a different supergroup to the current live infection. Mapping the origins of the insertions onto the filarial nematode phylogeny we derive a complex model of evolution of Wolbachia symbiosis. The history of association between Wolbachia and onchocercid nematodes includes not only cospeciation, as would be expected from a mutualist symbiosis, but also loss (in the 5 Wolbachia-free species), frequent symbiont replacement, and dual infection. This dynamic pattern is challenging to models that assume host–symbiont mutualism.

Main group pallasite meteorites (PMG) are samples of an early, highly differentiated magmatic planetesimal dominated by olivine and metal-sulfide-phosphide assemblages with accessory chromite among other phases. This mineralogy reflects mantle- and core-related reservoirs, but the relative contributions of each and the overall petrogenesis are obscured by high degrees of protolith melting. Here, we present new data on the chemistry of chromite in these meteorites and review previous datasets. The purely lithophile elements Mg and Al partition into chromite via (Mg,Fe)(Al,Cr)2O4 and mainly reflect interactions with olivine and basaltic melt, respectively. Chromite cores are virtually always more aluminous than rims, and while MgO contents were likely reset during slow cooling, their Al2O3 contents are more robust and were largely set during the period of silicate magmatism. Main group pallasite chromites display bimodality in Al2O3 contents, with peak concentrations at ~7.7 wt% and below 6 wt%, which is unlike any other achondrite chromite population. Some chromites have very low Al2O3 contents (~0.01 wt%) due to formation in the absence of silicate melt, that is, via exsolution of Cr from cooling liquid metal. High-, low-, and very low-Al2O3 chromites in these meteorites broadly reflect relict, prograde, and retrograde periods of planetesimal heating followed by cooling. The Al2O3 contents of the chromites in many other achondrites and equilibrated chondrites are similar to the higher values in pallasites, with most greater than 3 wt%. This suggests that meteoritic chromite is a significant sink for 26Al during its life as a heat source for planetesimal differentiation. To first order, it may be responsible for ~25%–50% (i.e., about one third) of heating in partially depleted mantles.