Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation

Previously, it has been reported that amine-PIM-1, a polymer of intrinsic microporosity obtained by reduction of nitrile groups of PIM-1 to primary amine groups, shows enhanced CO2 selectivity during mixed gas permeation studies with respect to single gas measurements for gas pairs involving CO2. This distinct and potentially useful behaviour was ascribed to the affinity of CO2 for the polymer amine groups. Here, we demonstrate that enhanced selectivity originates from both CO2 physisorption and chemisorption. A combination of 13C and 15N solid-state NMR spectroscopic analyses of a CO2-loaded amine-PIM-1 membrane allowed the identification and quantitative determination of both chemisorbed and physisorbed species and the characterization of polymer-CO2 interactions. Experiments with 13C isotopically enriched CO2 unequivocally demonstrated the conversion of 20% of the NH2 groups into carbamic acids at 298 K and a CO2 pressure of 1 bar. Chemisorption was supported by the strong heat of CO2 adsorption for amine-PIM-1 that was estimated as 50 kJ mol−1. Molecular dynamics simulations with models based on the experimentally determined polymer structure gave a detailed description of intra- and interchain hydrogen bond interactions in amine-PIM-1 after chemisorption, as well as of the effect of chemisorption on polymer porosity and physisorption

Professional Registration of Probation Practitioners in a Devolved Welsh Probation Service

In this paper, we consider the newly implemented Probation Professional Register Policy Framework in the context of the intent of the Welsh Government (WG) to work towards the devolution of justice, including probation. Thus, we reflect on devolution and its potential implications, the specific forms of partnership working and development in Wales, probation organisational culture, and questions of probation's legitimacy. We suggest that to make the most of the professional register's potential for professionalisation of probation practice, it needs to be embedded in an organisational structure and culture that fully owns and promotes the ethics and values of partnership working, taking a rights-based approach in the support for those who cause harm to victims and communities, and evidence-based practice

Oxygen isotope dendrochronology allows dating of historical timbers across a wide geographical region

We explore the applicability and geographic reach of two northwest European stable oxygen isotope (δ18O) chronologies for the precision dating of annually resolved δ18O series developed from late 15th-century oak (Quercus sp.) roof timbers from St. James’ Church in Bruges, Belgium. In doing so this study assesses ring-width dendrochronology and provenance analysis alongside oxygen isotope dendrochronology in Belgium and its surrounding regions.The δ18O-series of the historical timbers display a high internal coherence, allowing the construction of a mean isotope series (1325 to 1468 CE). Cross-dating against master chronologies for Central England, U.K. and Fontainebleau, France, provide reliable matches that surpass statistical thresholds and quality control measures, corroborating the dating results obtained from conventional ring-width dating.Oxygen stable isotope dendrochronology emerges as a valuable tool for precise dating of historical timber structures. This pilot study demonstrates the applicability of existing reference chronologies beyond their core regions and underscores its significance in cultural heritage studies. Despite the demanding nature of the technique in terms of time and expertise, the potential benefits warrant continued investment in expanding the temporal and geographic coverage of well-replicated oxygen isotope reference chronologies

Methodological reflections on tracing networked images

Purpose: Many scholars highlight a need for reflexive methodological accounts to support visual research. Therefore, this paper offers detailed reflection on the methods involved in tracing and analysing 248 commercial images of entrepreneurship. This account supports our published work examining entrepreneurial masculinities and femininities, which conceptualised the gendering of entrepreneurial aesthetics, and proposed the significance of image networks in the reproduction of neoliberal ideals. Design/Methodology/Approach:Now based on further methodological reflexivity we offer insights on both the possibilities and challenges of tracing networked images by reviewing four methodological complexities: reflexive engagement with online images; working with and across platforms; tracing as a potentially never-ending process; and montage approaches to analysis. Findings: Our account focuses on a specific form of imagery – commercial images – on a certain representation – the gendered entrepreneur – and on a particular complex site of encounter – online. This work mapped a visual repertoire of gendered entrepreneurship online by tracing visual constructions of entrepreneurial masculinity and femininity. In this paper we open the methodological ‘black box’ of our study and explain our belief that methodological advances can only be built through exposing our working practice. Originality: Through our detailed reflective account we aim to open discussions to aid development and use of complex visual methods online

Evaluation of a caesium fountain frequency standard for antihydrogen spectroscopy

The performance of a caesium fountain frequency reference for use in precision measurements of trapped antihydrogen in the ALPHA experiment at CERN is evaluated. A description of the fountain is provided together with a characterisation of systematic effects. The impact of the magnetic environment in the Antimatter Factory, where the fountain is installed, on the performance of the fountain is considered and shown to be insignificant. The systematic fractional frequency uncertainty of the fountain is 3.0 × 10−16. The short-term frequency stability of the measured frequency from the ALPHA-HM1 maser is 1.5 × 10−13τ−1/2, whereas the fountain itself shows a stability limit of 4.7 × 10−14τ−1/2. We find a fractional frequency difference of (1.0 ± 2.2 (stat.) ± 6.5 (syst.)) ×10−16 in a comparison with Terrestrial Time via a GNSS Common View satellite link between January 2023 and June 2024. The fountain enables a significant increase in frequency precision in antihydrogen spectroscopic measurements, and paves the way for improved limits on matter–antimatter comparisons

Sex‐Dependent Influence of Major Histocompatibility Complex Diversity on Fitness in a Social Mammal

Parasite infections affect males and females differently across a wide range of species, often due to differences in immune responses. Generally, females tend to have stronger immune defences and lower parasite loads than males. The major histocompatibility complex (MHC) plays a crucial role in the adaptive immune response, and extensive research has explored how variation in this region influences infection and fitness outcomes. However, studies of sex‐specific relationships between MHC variation and infection are scarce, perhaps because MHC genes are located on the autosomes, which are shared by both sexes. Here, we provide evidence of sexually antagonistic selection in a wild, group‐living mammal—the banded mongoose. Using genetic and life history data collected from over 300 individuals across 25 years, we found that both MHC class I (MHC‐I) and MHC class II (MHC‐II) diversity influence lifetime reproductive success differently in males and females. Specifically, higher MHC diversity is linked to increased fitness in males but decreased fitness in females. Furthermore, MHC diversity did not differ between the sexes, indicating an unresolved genetic sexual conflict. Our findings demonstrate that sexually antagonistic selection acts on the MHC and may operate across both MHC classes but differently. This study contributes to the growing body of evidence that sex is a significant factor in shaping host immunity and fitness

Conceptualising Programming Language Semantics

The semantics of programming languages tend to be discussed with high levels of formality; much of the previous research—both philosophical and historical—has investigated them from this perspective. In this paper, I draw on the philosophical and cognitive theories of metaphor and use the early work of Adriaan van Wijngaarden as a historical case study to explore the conceptual and discursive surroundings of semantics. I investigate the relationships between the texts of semantics, the abstract entities they denote, and the metaphors, analogies, and illustrative language used to accompany or explain the same. This serves to further understanding of the historical developments of work in this area, the nature of programming languages and their semantics, and the importance of the communicative methods used in dissemination and education of computer science

The Future of Conversation is Evolving from Human Dialogue to Hybrid Human-Agentic Discourse

In an era increasingly dominated by artificial intelligence (AI), the essence of human conversation is undergoing significant transformation. Once exclusively human, conversation is now increasingly mediated by AI agents, voice assistants, and digital platforms. This paper critically explores this profound shift, examining the nature and implications of hybrid human machine discourse. Addressing three fundamental questions, we interrogate what constitutes genuine conversation when one party lacks consciousness and emotion; how traditional norms of human dialogue translate into human-machine interactions; and what considerations developers and governance frameworks must prioritize in this evolving context. Building upon Nass and Brave’s (2005) concept of "voice activation," which demonstrates humans’ inherent social responses toward artificial speech, this study identifies the dual promise and peril of conversational AI, emphasizing the risks of confusion, over-trust, and emotional misdirection. Arguing that AI-driven dialogue is not merely automation but a profound cultural and ethical shift, this research advocates for new literacies, ethical frameworks, and a re-evaluation of what authentic communication entails. By tracing the philosophical roots and current technological practices of conversation, the study underscores the urgency of rethinking communication ethics, literacy, and practice in our increasingly hybrid human-machine conversational landscap