Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane

A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60–145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments

Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane

A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit a broad range of glass-transition temperatures (Tg 60–145 °C). These polyesters are amenable to further postpolymerization functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addition experiments

One size does not fit all - stroke survivor's views on group self-management interventions

INTRODUCTION: Stroke is the main cause of complex disability in the UK. Many stroke survivors feel abandoned when rehabilitation ends and more than half are left with long-term unmet needs. There is now emerging interest in whether group self-management programs (SMP) specifically for stroke survivors could help. However, more work is required to understand the acceptability of group SMPs to stroke survivors and the factors of concern that could impact efficacy. PURPOSE: The purpose of this study is to explore stroke survivor's views on (1) possible benefits of a group SMP, (2) possible challenges of a group SMP, and (3) when/where to implement a SMP in an individual's stroke journey. METHOD: Fourteen stroke survivors took part in semi-structured interviews, which were analyzed using an inductive thematic approach. RESULTS: Three main themes were identified in the data: (1) a space to share support, (2) it is not a one size fits all problem, and (3) how is it all going to happen? CONCLUSION: A varied group of stroke survivors can provide valuable insight and ideas about how group SMP's should be constructed. To the best of our knowledge, this is the first patient engagement study that explores group SMPs for stroke. In future work, researchers may find it helpful to consider the findings from this study to inform the design of group SMPs. Implications for Rehabilitation There is interest in whether unmet needs after stroke could be addressed through a group self-management program (SMP). Stroke survivors can provide valuable insight and ideas about how group SMPs should be constructed. Group SMPs should carefully consider: how to create a safe space in which stroke survivors feel comfortable, the impact of the facilitators, tailoring the group to the individual, the presence of carers, and the emotional impact of a group SMP

d-Xylose oxetane copolymers as bioderived and tuneable polyesters for amorphous solid dispersions

The ring-opening copolymerisation of cyclic anhydrides with an oxetane derived from natural monosaccharide D-xylose has been used to synthesise fully biobased water soluble polyesters, which are able to stabilise the amorphous phases of nifedipine and mefenamic acid, enhancing their apparent solubility in water up to 918 and 142% respectively. 2D picolitre-scale inkjet-printing, coupled with polarised optical microscopy (POM) analysis, enabled an initial, high-throughput miniaturised (ng–μg scale) screening of drug formulations. The best formulations were scaled up and analysed by FT-IR spectroscopy and DSC, revealing interactions between the drugs and polymers. Finally, drug dissolution studies demonstrated the effectiveness of the polymers in improving the drugs’ apparent solubility in water. These results showcase the potential of synthetic carbohydrate polymers as excipient for tailored drug formulations

The Natural Products Atlas 2.0 : a database of microbially-derived natural products

Within the natural products field there is an increasing emphasis on the study of compounds from microbial sources. This has been fuelled by interest in the central role that microorganisms play in mediating both interspecies interactions and host-microbe relationships. To support the study of natural products chemistry produced by microorganisms we released the Natural Products Atlas, a database of known microbial natural products structures, in 2019. This paper reports the release of a new version of the database which includes a full RESTful application programming interface (API), a new website framework, and an expanded database that includes 8128 new compounds, bringing the total to 32 552. In addition to these structural and content changes we have added full taxonomic descriptions for all microbial taxa and have added chemical ontology terms from both NP Classifier and ClassyFire. We have also performed manual curation to review all entries with incomplete configurational assignments and have integrated data from external resources, including CyanoMetDB. Finally, we have improved the user experience by updating the Overview dashboard and creating a dashboard for taxonomic origin. The database can be accessed via the new interactive website at https://www.npatlas.org.Peer reviewe

'To live and die [for] Dixie': Irish civilians and the Confederate States of America

Around 20,000 Irishmen served in the Confederate army in the Civil War. As a result, they left behind, in various Southern towns and cities, large numbers of friends, family, and community leaders. As with native-born Confederates, Irish civilian support was crucial to Irish participation in the Confederate military effort. Also, Irish civilians served in various supporting roles: in factories and hospitals, on railroads and diplomatic missions, and as boosters for the cause. They also, however, suffered in bombardments, sieges, and the blockade. Usually poorer than their native neighbours, they could not afford to become 'refugees' and move away from the centres of conflict. This essay, based on research from manuscript collections, contemporary newspapers, British Consular records, and Federal military records, will examine the role of Irish civilians in the Confederacy, and assess the role this activity had on their integration into Southern communities. It will also look at Irish civilians in the defeat of the Confederacy, particularly when they came under Union occupation. Initial research shows that Irish civilians were not as upset as other whites in the South about Union victory. They welcomed a return to normalcy, and often 'collaborated' with Union authorities. Also, Irish desertion rates in the Confederate army were particularly high, and I will attempt to gauge whether Irish civilians played a role in this. All of the research in this paper will thus be put in the context of the Drew Gilpin Faust/Gary Gallagher debate on the influence of the Confederate homefront on military performance. By studying the Irish civilian experience one can assess how strong the Confederate national experiment was. Was it a nation without a nationalism