bluuebunny/crossref_metadata_2025_split huggingface dataset:
Copper(II)‐Amine Complex‐Mediated Intramolecular Coupling of Gallates: A Bioinspired Solution to the Atroposelective Synthesis of Ellagitannins
Authors: Larrieu Romain , Richieu Antoine , Cornu Anaëlle , Daugey Nicolas , Pouységu Laurent , Deffieux Denis , Quideau Stéphane 
Published: September 2024

AbstractTotal syntheses of the C‐glucosidic ellagitannins (−)‐punicacortein A, (−)‐epipunicacortein A and (+)‐castalin were accomplished for the first time, and those of the glucopyranosic ellagitannins (+)‐tellimagrandin I and (+)‐pedunculagin were revisited. The atroposelective construction of their characteristic hexahydroxydiphenoyl (HHDP) and nonahydroxyterphenoyl (NHTP) units relied on the use of different cupric‐amine complexes under different reaction conditions to mediate the intramolecular dehydrogenative coupling of galloyl groups at different positions of glucose cores. In particular, the monodentate n‐butylamine and the bidentate (−)‐sparteine were found to be complementary in their capacity to promote the regio‐ and atroposelective coupling of galloyl groups on a 4C1‐glucopyranosic core into 2,3‐O‐(S)‐ and/or 4,6‐O‐(S)‐HHDP units. Furthermore, replacing (−)‐sparteine by its optical antipode not only counteracted the substrate‐controlled induction of atroposelectivity to forge a 4,6‐O‐(R)‐HHDP unit, but it also enabled a 4C1 to 1C4 ring flip of the glucopyranosic core and hence the formation of 2,4‐O‐(R)‐ and 3,6‐O‐(R)‐HHDP units, such as those featured in the glucopyranosic ellagitannins phyllanemblinin B and geraniin.
Cyclische Acetale als expandierende Monomer zur Verringerung von Schrumpfung
Authors: Ricke Alexander , Berk Oskar , Koch Thomas , Liska Robert , Baudis Stefan 
Published: September 2024

AbstractUmpolungskatalysatoren (PRCs) für Wasserstoff‐Übertragungsreaktionen sind innerhalb der Radikalchemie seit mehr als 60 Jahren bekannt, werden allerdings im Bereich der Photopolymerisation bisher kaum beschrieben und genutzt. In diesem Artikel demonstrieren wir die Verwendung von Thiolen in einer einzigartigen Doppelfunktion als Thiol‐En‐Click‐Reagenzien und Umpolungskatalysatoren (PRC) für radikalvermittelte Redox‐Umlagerungsreaktionen von Benzylidenacetalen. Während der Umlagerungsreaktionen wandeln sich Benzylidenacetale in Benzoesäureester um, wodurch es zu einer signifikanten Volumenssteigerung kommt, die der Schrumpfung des Duromeren entgegenwirkt. Wir konnten zeigen, dass diese Expansion auf molekularer Ebene Schrumpfungs‐ und Polymerisationsspannungen reduziert ohne die (thermo‐) mechanischen Eigenschaften des Polymernetzwerkes wesentlich zu beeinflussen. Der Hauptvorteil dieser Herangehensweise liegt dabei in der Schlichtheit, da hier keine Additive wie Sensibilisatoren oder unterschiedliche Initiatorsysteme (radikalisch und kationisch) notwendig sind. Des Weiteren kann dieselbe Lichtquelle sowohl für die Polymerisation als auch für die Expansion im Zuge der Umlagerungsreaktion genutzt werden. Zusätzlich erlaubt der verwendete Photoinitiator eine Kontrolle der Polymerisation über Raum und Zeit, wodurch sich dieses System als hervorragende Grundlage zur additiven Fertigung anbietet.
Transforming Aryl‐Tetrazines into Bioorthogonal Scissors for Systematic Cleavage of trans‐Cyclooctenes
Authors: Wilkovitsch Martin , Kuba Walter , Keppel Patrick , Sohr Barbara , Löffler Andreas , Kronister Stefan , del Castillo Andres Fernandez , Goldeck Marion , Dzijak Rastislav , Rahm Michal , Vrabel Milan , Svatunek Dennis , Carlson Jonathan C. T. , Mikula Hannes 
Published: September 2024

AbstractBioorthogonal bond‐cleavage reactions have emerged as a powerful tool for precise spatiotemporal control of (bio)molecular function in the biological context. Among these chemistries, the tetrazine‐triggered elimination of cleavable trans‐cyclooctenes (click‐to‐release) stands out due to high reaction rates, versatility, and selectivity. Despite an increasing understanding of the underlying mechanisms, application of this reaction remains limited by the cumulative performance trade‐offs (i.e., click kinetics, release kinetics, release yield) of existing tools. Efficient release has been restricted to tetrazine scaffolds with comparatively low click reactivity, while highly reactive aryl‐tetrazines give only minimal release. By introducing hydroxyl groups onto phenyl‐ and pyridyl‐tetrazine scaffolds, we have developed a new class of ‘bioorthogonal scissors’ with unique chemical performance. We demonstrate that hydroxyaryl‐tetrazines achieve near‐quantitative release upon accelerated click reaction with cleavable trans‐cyclooctenes, as exemplified by click‐triggered activation of a caged prodrug, intramitochondrial cleavage of a fluorogenic probe (turn‐on) in live cells, and rapid intracellular bioorthogonal disassembly (turn‐off) of a ligand‐dye conjugate.
High‐Resolution Ensemble Modelling of Coral Distributions in the Northern Gulf of Mexico Based on Geomorphometry: Coral Diversity and Benthic Habitat Fragmentation From Oil and Gas Infrastructure to Inform Spatial Planning
Authors: Lecours Vincent , Oxton Amy , Khor Danny , Tiplea Julia 
Published: September 2024

ABSTRACTThe northern Gulf of Mexico is home to several species of corals that provide a wide range of ecosystem services to other organisms. Oil and gas infrastructure, such as platforms and pipelines, form an extensive network throughout the northern Gulf of Mexico. Detrimental impacts associated with oil and gas exploration and extraction have been recorded in this area at depths where corals are found. Due to these ecosystems' vulnerability to long‐term impacts, it is necessary to determine areas of interest that would benefit from further exploration and informed spatial planning. This study aimed to identify potential areas of interest for coral studies in the northern Gulf of Mexico. Ensemble species distribution models for 13 species of corals including scleractinians, black corals, and octocorals were produced based on seafloor characteristics and combined to identify areas with relatively higher coral diversity potential than others. The ensemble modelling approach produced robust outputs, as evaluated by the area under the curve, Cohen's kappa coefficient, sensitivity, specificity and the proportion of correct predictions. The proximity of suitable habitat to active and proposed oil and gas infrastructure was evaluated; this spatial analysis showed that oil and gas infrastructures potentially impact 23.5% of all predicted suitable coral habitat in the study area and contribute to benthic habitat fragmentation. Twelve areas of interest greater than 100 km2 and located outside a 4‐km zone of potential influence from oil and gas infrastructure were delineated and deemed of interest for further exploration and spatial planning, and hypothetical prioritization scenarios for spatial planning are presented. The maps produced can inform discussions among stakeholders to reach the best spatial planning outcomes while considering other ecological, social, economic and governance factors.
MOF Derived Ni‐Cu Double Hydroxide Based Self‐Powered Flexible Asymmetric Supercapacitor Using Onion Scale as an Effective Bio‐Piezoelectric Separator
Authors: Maity Parna , Maitra Anirban , Ojha Suparna , Mondal Ankita , Bera Aswini , Bera Sumanta , Das Arkapriya , Bhusan Khatua Bhanu 
Published: September 2024

AbstractModern electronic devices necessitate the utilization of compact, wearable, and flexible substrates capable of simultaneously harvesting and storing energy by merging traditional energy harvesting techniques with storage mechanisms into a singular portable device. Here, we present the fabrication of a low‐cost, sustainable, all‐solid‐state, self‐powered flexible asymmetric supercapacitor (SPASC) device. This device features MOF‐derived nickel‐copper double hydroxide nanosheets coated stainless steel (SS) fabric sheet (NCDH@SS) as the positive electrode, while manganese dioxide decorated activated porous carbon on SS fabric sheet (MnO2‐APC@SS) acts as the negative electrode. The electrodes are isolated by a PVA‐KOH gel electrolyte, while onion scale, a bio‐piezoelectric separator, ensures effective separation. The self‐charging ability of the device is demonstrated through mechanical deformation induced by finger imparting. This rectification‐free SPASC device exhibits remarkable performance, achieving a charge up to ∼235.41 mV from the preliminary open circuit voltage of ∼20.89 mV within 180 s under ∼16.25 N of applied compressive force (charged up to ∼214.52 mV). Furthermore, three SPASC devices connected in series can power up various portable electronic devices like wristwatches, calculators, and LEDs upon frequent imparting. Our work thus demonstrates an innovative and advanced approach towards the development of sustainable, flexible, and advanced self‐powered electronics.
Unreliable association between self‐reported sense of direction and peripheral vestibular function
Authors: Gerb J. , Brandt T. , Dieterich M. 
Published: September 2024

AbstractBackgroundUni‐ or bilateral peripheral vestibular impairment causes objective spatial orientation deficits, which can be measured using pen‐and‐paper‐tests or sensorimotor tasks (navigation or pointing). For patients’ subjective orientation abilities, questionnaires are commonly used (e.g., Santa Barbara sense of direction scale [SBSODS]). However, the relationship between subjective assessment of spatial skills and objective vestibular function has only been scarcely investigated.MethodsA total of 177 patients (mean age 57.86 ± 17.53 years, 90 females) who presented in our tertiary Center for Vertigo and Balance Disorders underwent neuro‐otological examinations, including bithermal water calorics, video head impulse test (vHIT), and testing of the subjective visual vertical (SVV), and filled out the SBSODS (German version). Correlation analyses and linear multiple regression model analyses were performed between vestibular test results and self‐assessment scores. Additionally, groupwise vestibular function for patients with low, average, and high self‐report scores was analyzed.ResultsForty‐two patients fulfilled the diagnostic criteria for bilateral vestibulopathy, 93 for chronic unilateral vestibulopathy (68 unilateral caloric hypofunction and 25 isolated horizontal vestibulo‐ocular reflex deficits), and 42 patients had normal vestibular test results. SBSODS scores showed clear sex differences with higher subjective skill levels in males (mean score males: 4.94 ± 0.99, females 4.40 ± 0.94; Student's t‐test: t‐3.78, p < .001***). No stable correlation between objective vestibular function and subjective sense of spatial orientation was found. A multiple linear regression model could not reliably explain the self‐reported variance. The three patient groups with low, average, and high self‐assessment‐scores showed no significant differences of vestibular function.ConclusionSelf‐reported assessment of spatial orientation does not robustly correlate with objective peripheral vestibular function. Therefore, other methods of measuring spatial skills in real‐world and virtual environments are required to disclose orientation deficits due to vestibular hypofunction.
Fostering circular economy in small and medium‐sized enterprises: The role of social capital, adaptive capacity, entrepreneurial orientation and a pro‐sustainable environment
Authors: Alcalde‐Calonge Alberto , Ruiz‐Palomino Pablo , Sáez‐Martínez Francisco José 
Published: September 2024

AbstractThis study addresses the challenges faced by small‐ and medium‐sized enterprises (SMEs) in undertaking sustainability projects due to limited resources and explores the factors influencing SMEs' adoption of circular economy (CE) practices, an area under‐researched in literature. Analysing data from 205 SMEs in Spain's forest bioeconomy sector using fuzzy sets (fs/QCA), the study finds that internal and external social capital, coupled with adaptive capacity, are crucial influences, particularly when SMEs exhibit an entrepreneurial culture. Conversely, if SMEs do not have an entrepreneurial orientation or the environment is not pro‐sustainable, these three characteristics may lead to low CE adoption. Thus, the study emphasizes SMEs' imperative to cultivate social capital, enhance adaptive capacity, and embrace innovation and risk‐taking to leverage internal and external resources and meet environmental demands, thereby reducing costs and time in adopting CE practices. Additionally, it underscores policymakers' pivotal role in fostering a pro‐sustainable environment, being critical for SME engagement in CE practices.
Factors impacting hospitalisation and related health service costs in cancer survivors in Australia: Results from a population data linkage study in Queensland (COS‐Q)
Authors: Merollini Katharina M. D. , Collins Louisa G. , Jones Andrew T. , Aitken Joanne F. , Kimlin Michael G. 
Published: September 2024

AbstractBackgroundThe global economic cost of cancer and the costs of ongoing care for survivors are increasing. Little is known about factors affecting hospitalisations and related costs for the growing number of cancer survivors. Our aim was to identify associated factors of cancer survivors admitted to hospital in the public system and their costs from a health services perspective.MethodsA population‐based, retrospective, data linkage study was conducted in Queensland (COS‐Q), Australia, including individuals diagnosed with a first primary cancer who incurred healthcare costs between 2013 and 2016. Generalised linear models were fitted to explore associations between socio‐demographic (age, sex, country of birth, marital status, occupation, geographic remoteness category and socio‐economic index) and clinical (cancer type, year of/time since diagnosis, vital status and care type) factors with mean annual hospital costs and mean episode costs.ResultsOf the cohort (N = 230,380) 48.5% (n = 111,820) incurred hospitalisations in the public system (n = 682,483 admissions). Hospital costs were highest for individuals who died during the costing period (cost ratio ‘CR’: 1.79, p < 0.001) or living in very remote or remote location (CR: 1.71 and CR: 1.36, p < 0.001) or aged 0–24 years (CR: 1.63, p < 0.001). Episode costs were highest for individuals in rehabilitation or palliative care (CR: 2.94 and CR: 2.34, p < 0.001), or very remote location (CR: 2.10, p < 0.001). Higher contributors to overall hospital costs were ‘diseases and disorders of the digestive system’ (AU$661 m, 21% of admissions) and ‘neoplastic disorders’ (AU$554 m, 20% of admissions).ConclusionsWe identified a range of factors associated with hospitalisation and higher hospital costs for cancer survivors, and our results clearly demonstrate very high public health costs of hospitalisation. There is a lack of obvious means to reduce these costs in the short or medium term which emphasises an increasing economic imperative to improving cancer prevention and investments in home‐ or community‐based patient support services.
Understanding causes of adolescents' ascriptions of peers' dual ethnic and national belonging
Authors: Schlette Anniek , Stark Tobias H. , Smeekes Anouk , Lubbers Marcel 
Published: September 2024

AbstractDescendants of migrants often feel belonging to the ethnic minority group of their parents and the national group (i.e., dual identifiers). If second‐generation migrants are recognized as members of both groups, they can create social bridges and improve intergroup relations. However, people often ascribe them only minority belonging, thereby not recognizing dual belonging. Following the social identity approach, we examined who ascribes dual belonging to second‐generation migrants and why they do so. We focus on the role of national self‐identification, and endorsing a civic or ethnic conception of nationhood on the ascriptions that national majority members make to their second‐generation peers. We collected sociometric data from secondary vocational school classes in the Netherlands (Nstudents = 397, Nclasses = 36). Findings replicated that many second‐generation migrants self‐identified as dual (69%), but only a small number of dual ascriptions were given to them (15%). Although we found no effects for the hypothesized relations on ascribing only minority rather than dual belonging, national majority members who had a stronger national identification displayed a stronger tendency to ascribe only national rather than dual belonging. This raises the question whether dual identifiers could act as ‘gateway groups’ to improve intergroup relations.
On the Challenges to Develop Hybrid Faradaic‐Capacitive Electrodes Incorporating a Sacrificial Salt for Lithium‐ion Capacitors: The Case of Li3V1.95Ni0.05(PO4)3‐AC‐Li2C4O4
Authors: Granados‐Moreno Miguel , Arnaiz Maria , Gucciardi Emanuele , Enkubahri Asres Nahom , Goikolea Eider , Ajuria Jon 
Published: September 2024

AbstractThe low capacity of activated carbon (AC) electrodes remains as one of the major limiting factors for the development of high energy density lithium‐ion capacitors (LICs). Hybridization of capacitive AC electrodes by incorporating faradaic materials into the electrode formulation could be performed to enhance the capacity of the overall device. However, this strategy requires an accurate electrode design to maximize the performance. In this work, Li3V1.95Ni0.05(PO4)3 (LVNP) was selected as faradaic material due to its compatibility with AC, showing high capacity, fast ionic diffusion, and relatively high conductivity. Various formulations and mass loadings have been studied to analyze the impact of incorporating LVNP into the positive electrode on the performance of the hybrid electrode. Moreover, for practical LIC applications, a sacrificial salt ‐dilithium squarate, Li2C4O4‐ was included in the hybrid electrode as a pre‐lithiation additive, developing a ternary electrode. The sacrificial salt oxidized releasing lithium ions, while the electrochemical performance of the hybrid positive electrode remained almost unaltered. Finally, a cycle life test combined with a post‐mortem analysis allows understanding the failure mechanisms of the electrode, suggesting the need of further improvements of the electrolyte and electrode‐electrolyte interface to develop long lifetime hybrid faradaic‐capacitive electrodes based on LVNP‐AC active materials.
Intramolecular Pericyclic Re‐hydroboration via Six‐Membered Transition State: Synthesis of Fused Borolo[3,2‐b]siloles
Authors: Tok Oleg L. , Bavol Dmytro , Bould Jonathan 
Published: September 2024

AbstractWe experimentally demonstrate a new type of the intramolecular reaction between non‐activated alkyne units and the dialkylboryl group (9‐BBN), which was previously only hypothesized and studied on a calculational level. The reaction described here can formally be classified as a 1,2‐hydroboration reaction, but, in contrast to the classical mechanism via a cyclic four‐membered transition state, the reaction proceeds by a pericyclic mechanism involving a six‐membered transition state. In practice, the reaction allows the synthesis of a new class of the borolenes fused with silole or dihydrosilole units. Thus, the heating (125 °C) of 2,3‐dihydrosiloles or 2,3‐dihydrosilolo[2,3‐b]silole bearing 9‐BBN and propargyl or dimethylpropargyl groups in positions 4 and 5, respectively, affords, in high to moderate yields, di‐ and tricyclic compounds containing a borolo[3,2‐b]silole unit. In all cases, the reactions are accompanied by an unprecedented dehydroboration of the 9‐BBN fragment, leading, in the final products, to a cyclooct‐4‐enyl group on the boron atom. The effects of the substituents on the rate and the selectivity of the reaction are discussed. The structures of all the new compounds have been determined from HRMS together with multinuclear 1D and 2D NMR spectroscopy, the results of which are in excellent agreement with DFT calculated chemical shifts.
Empirical prediction on boilover onset and impact for liquid hydrocarbon fire in atmospheric storage tank
Authors: Buang Azizul , Zaaba Muhammad Ameer , Yusof Muhammad Izham Mohd , Manogaran Daneskumar , Hifni Hani Tiara Faihana , Bilad Muhammad Roil 
Published: September 2024

AbstractBoilover can occur several hours after the fuel in a storage tank caught fire. The delayed occurrence is an unknown strong parameter when managing the emergency response operations. Those managing response operations must be aware of the boilover potential and take the precautions to ensure safety. Modelling the phenomenon enables predicting crucial event features and assists in highlighting safety measures, with a key focus on the ignition‐to‐boilover time interval. This study focused on the predictive empirical tool development aimed at estimating the boilover onset time and consequences. This was achieved through series of small‐scale boilover experiments, followed by validation using cases of boilover incidents. The results revealed a linear relationship between the boilover onset time and the initial depth of fuel. Consequently, an empirical correlation was derived to predict the time to boilover. The developed correlation has demonstrated its ability to offer conservative predictions while also exhibiting agreement with both the observed onset time and consequences of boilover events. The reported time to boilover for the Czechowice‐Dziedzice incident is 1050 min, while the predicted time is 1413.2 min. The model showed reasonable agreement with the Amoco Refinery incident. The predicted boilover time of 811.3 min aligns with the boilover incident, reported as 790 and 925 min, respectively. It is evident that the empirical model can predict the time to boilover to a similar order of magnitude. Certain considerations in the development of effective strategies in handling fire scenario with boilover potentials can be assessed using the predictive tool developed.