bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tuning Transition Metal‐Containing Molecular Magnets by On‐Surface Polymerization
Authors: Baranowski Daniel , Cojocariu Iulia , Schio Luca , Bolaños Carolina Gutiérrez , Floreano Luca , Dreiser Jan , Carlotto Silvia , Casarin Maurizio , Feyer Vitaliy , Schneider Claus Michael 
Published: May 2024

AbstractPorphyrins are promising multifunctional units particularly interesting for the realization of molecular nanodevices. Their structural variety allows to create precursors suitable for the on‐surface polymerization of porphyrin blocks. The corresponding increased stability and improved transport properties of the formed polymerized molecular nanostructures make them practically worthwhile. For the case of 2D porphyrin materials, the effect of polymerization on the magnetic properties of transition metal ions has not been reported yet. Therefore, details on the properties of an extended covalent nickel tetraphenylporphyrin network formed via Ullmann coupling on the Cu(111) surface are reported. By using photoelectron and absorption spectroscopies together with density functional theory calculations, it is systematically evolving how the functional properties of the Ni centers are changed within a polymerized molecular structure in comparison to single‐molecule nickel tetraphenylporphyrin derivatives that build the 2D molecular network. A model that explains the differences in the electronic and magnetic properties observed for the Ni centers in both structures based on the additional rigidity characteristic of the molecular layer after polymerization is drawn.
Unveiling the Potential of Covalent Organic Frameworks for Energy Storage: Developments, Challenges, and Future Prospects
Authors: Dubey Prashant , Shrivastav Vishal , Boruah Tribani , Zoppellaro Giorgio , Zbořil Radek , Bakandritsos Aristides , Sundriyal Shashank 
Published: May 2024

AbstractCovalent organic frameworks (COFs) are porous structures emerging as promising electrode materials due to their high structural diversity, controlled and wide pore network, and amenability to chemical modifications. COFs are solely composed of periodically arranged organic molecules, resulting in lightweight materials. Their inherent properties, such as extended surface area and diverse framework topologies, along with their high proclivity to chemical modification, have positioned COFs as sophisticated materials in the realm of electrochemical energy storage (EES). The modular structure of COFs facilitates the integration of key functions such as redox‐active moieties, fast charge diffusion channels, composite formation with conductive counterparts, and highly porous network for accommodating charged energy carriers, which can significantly enhance their electrochemical performance. However, ascribing intricate porosity and redox‐active functionalities to a single COF structure, while maintaining long‐term electrochemical stability, is challenging. Efforts to overcome these hurdles embrace strategies such as the implementation of reversible linkages for structural flexibility, stimuli‐responsive functionalities, and incorporating chemical groups to promote the formation of COF heterostructures. This review focuses on the recent progress of COFs in EES devices, such as batteries and supercapacitors, through a meticulous exploration of the latest strategies aimed at optimizing COFs as advanced electrodes in future EES technologies.
An overview of the history, role, and struggles of agricultural economics and business programs at 1890 Land‐Grant Historically Black Colleges and Universities (HBCU)
Authors: Grant Jared , Lachaud Michée A. , Solís Daniel 
Published: May 2024

AbstractBlacks have been systematically under‐represented in the Agricultural Economics profession, representing only 7% of agricultural economists in academia and between 5% and 10% in the private and public sectors, respectively. Although different policies and funding strategies have been implemented to increase the representation of minorities in the profession, these numbers have not shown significant improvements over time. This paper provides an overview of the history, role, and struggles of 1890 Land‐Grant Historically Black Colleges and Universities in general, and in particular, their agricultural economics and business (AEB) Programs. Recommendations and thoughts on how to increase diversity in AEB programs are also discussed.
Genome size variation in Cape schoenoid sedges (Schoeneae) and its ecophysiological consequences
Authors: van Mazijk Ruan , West Adam G. , Verboom G. Anthony , Elliott Tammy L. , Bureš Petr , Muasya A. Muthama 
Published: May 2024

AbstractPremiseIncreases in genome size in plants—often associated with larger, low‐density stomata and greater water‐use efficiency (WUE)—could affect plant ecophysiological and hydraulic function. Variation in plant genome size is often due to polyploidy, having occurred repeatedly in the austral sedge genus Schoenus in the Cape Floristic Region (CFR), while species in the other major schoenoid genus in the region, Tetraria, have smaller genomes. Comparing these genera is useful as they co‐occur at the landscape level, under broadly similar bioclimatic conditions. We hypothesized that CFR Schoenus have greater WUE, with lower maximum stomatal conductance (gwmax) imposed by larger, less‐dense stomata.MethodsWe investigated relationships between genome size and stomatal parameters in a phylogenetic context, reconstructing a phylogeny of CFR‐occurring Schoeneae (Cyperaceae). Species’ stomatal and functional traits were measured from field‐collected and herbarium specimens. Carbon stable isotopes were used as an index of WUE. Genome size was derived from flow‐cytometric measurements of leafy shoots.ResultsEvolutionary regressions demonstrated that stomatal size and density covary with genome size, positively and negatively, respectively, with genome size explaining 72–75% of the variation in stomatal size. Larger‐genomed species had lower gwmax and C:N ratios, particularly in culms.ConclusionsWe interpret differences in vegetative physiology between the genera as evidence of more‐conservative strategies in CFR Schoenus compared to the more‐acquisitive Tetraria. Because Schoenus have smaller, reduced leaves, they likely rely more on culm photosynthesis than Tetraria. Across the CFR Schoeneae, ecophysiology correlates with genome size, but confounding sources of trait variation limit inferences about causal relationships between traits.
High prevalence of iron deficiency and socioeconomic disparities in laboratory screening of non‐pregnant females of reproductive age: A retrospective cohort study
Authors: Wen Sophia , Nisenbaum Rosane , Weyand Angela C. , Tang Grace H. , Auerbach Michael , Sholzberg Michelle 
Published: May 2024

AbstractIron deficiency anemia (IDA) and non‐anemic iron deficiency (NAID) are highly prevalent among non‐pregnant females of reproductive age. Canada has no national screening guidelines for this population. Screening, when performed, is often with a complete blood count alone without ferritin or iron indices. The primary objective was to determine the prevalence of screening for NAID and IDA over a 3‐year period in non‐pregnant females of reproductive age who had tests performed at outpatient laboratories in Ontario, Canada. Retrospective cohort study of non‐pregnant females ages 15–54 in Ontario, from 2017 to 2019. NAID was defined as ferritin <30 μg/L, anemia as hemoglobin <120 g/L, and IDA as ferritin <30 μg/L and hemoglobin <120 g/L. Annual household income was estimated using patient postal codes. A total of 784 132 non‐pregnant females were included. The 82.1% were screened for iron deficiency, 38.3% had NAID and 13.1% had IDA; 55.6% with IDA had normal mean corpuscular volumes. The median household income was $89454.80 compared with a provincial median of $65285.00. Patients in the lowest income quintile had the highest odds of being anemic, and the lowest odds of having a ferritin checked. A large proportion of non‐pregnant females of reproductive age in this cohort were screened for iron deficiency. In this relatively privileged cohort, NAID affected nearly 40%, and IDA 13%. Most patients with IDA did not have microcytosis. Low household income was associated with the greatest odds of anemia and the lowest odds of being screened, highlighting inequitable access to screening for IDA in Ontario, Canada.
Electrocatalytic Formal C(sp2)−H Alkylations via Nickel‐Catalyzed Cross‐Electrophile Coupling with Versatile Arylsulfonium Salts
Authors: Michiyuki Takuya , Homölle Simon L. , Pandit Neeraj K. , Ackermann Lutz 
Published: May 2024

AbstractProducing sp3‐hybridized carbon‐enriched molecules is of particular interest due to their high success rate in clinical trials. The installation of aliphatic chains onto aromatic scaffolds was accomplished by nickel‐catalyzed C(sp2)−C(sp3) cross‐electrophile coupling with arylsulfonium salts. Thus, simple non‐prefunctionalized arenes could be alkylated through the formation of aryldibenzothiophenium salts. The reaction employs an electrochemical approach to avoid potentially hazardous chemical redox agents, and importantly, the one‐pot alkylation proved also viable, highlighting the robustness of our approach.
A Stable Chichibabin Diradicaloid with Near‐Infrared Emission
Authors: Chang Xingmao , Arnold Mona E. , Blinder Rémi , Zolg Julia , Wischnat Jonathan , van Slageren Joris , Jelezko Fedor , Kuehne Alexander J. C. , von Delius Max 
Published: May 2024

AbstractConjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM‐TTM diradicaloid, which exhibits high diradical character, a striking sky‐blue color and near‐infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in “just the right positions”, allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In‐depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.
Peri‐operative management and analgesic strategy for a patient undergoing quadruple limb amputation
Authors: Fenton‐May L. , Irvine M. , Huckle D. , Carter P. 
Published: May 2024

SummaryInadequately managed amputation pain can contribute to postoperative morbidity and mortality. However, amputation pain can be challenging to manage due to its complex nature, with both central and peripheral nociceptive and neuropathic elements. Here, we present the case of a 47‐year old man who developed irreversible ischaemic injuries to all four limbs following admission to intensive care with sepsis. He required quadruple amputation and we describe our approach to his peri‐operative management including anaesthesia, invasive monitoring and the multi‐modal approach to his peri‐operative management using a combination of intravenous analgesics, bilateral brachial plexus nerve catheters and a combined spinal and epidural. The patient made a good recovery and was able to return home from a rehabilitation facility 12 months after the operation, able to undertake many tasks himself with the aid of prosthetics.
Biological properties of 4‐trifluoromethylbenzyloxy‐substituted cobalt phthalocyanine‐gold nanoparticle conjugates
Authors: Göller İrem , Yenilmez H. Yasemin , Farajzadeh Öztürk Nazlı 
Published: May 2024

In this article, peripheral and non‐peripheral cobalt phthalocyanines (2 and 3) were synthesized and characterized by applying the spectroscopic methods (FT‐IR, 1H NMR, 13C NMR, Maldi‐Toff mass, and UV–vis). The synthesized compounds were used for the surficial modification of gold nanoparticles (AuNP). The novel conjugates (2‐AuNP and 3‐AuNP) were characterized using transmission electron microscopy. The antioxidant activities of bioagents (2, 3, 2‐AuNP, 3‐AuNP, and AuNP) were examined by performing three different methods, and the results were compared. When their antioxidant properties were examined, it was shown that the capacities of phthalocyanines were higher compared with the modified gold nanoparticles. In addition, antibacterial analysis of the compounds was carried out by applying two different methods. As a result of the analysis, it was determined that both cobalt phthalocyanines and nanoconjugates showed antibacterial activities against Escherichia coli. Phthalocyanine compounds showed lower IC50 results than phthalocyanine‐modified gold nanoparticles, while unmodified gold nanoparticles showed no α‐glucosidase inhibitory activity.
Study of the synthetic silica functionalization effect on wettability of oxidized polypropylene film by plasma discharge
Authors: Fantatho Felipe , Morales Ana Rita 
Published: May 2024

AbstractThis work describes the effect of functionalized silica, treated with organosilane (γ‐methacryloxypropyltrimethoxysilane), on the wettability loss of polypropylene (PP) film when exposed to surface oxidization treatment by atmospheric air plasma. The observed wettability loss results from the spontaneous process within the polymer matrix, which reduces surface energy, causing oxidized polymer molecules to move toward the bulk of the film. The effect of silica's functionalization on the initial wettability of oxidized PP film and its loss on storage time is measured by contact angle. Elemental analysis of the modified silica, employing acid catalytic processes, reveals the highest functionalization yield. Silicon nuclear magnetic resonance shows that the post‐condensation process negatively affects structures formed by the organosilane, eliminating three‐dimensional bonds and reverting it to its original and hydrolyzed state. The solvent extraction process and elemental analysis confirm that the concentration of organosilane in the chemically bonded layer, which was around 9 wt%, is not influenced by the post‐condensation treatment. Notably, silica functionalized with the highest concentration of organosilane has significantly improved initial wettability when oxidative treatment occurs within a shorter residence time (30 s), which achieved a contact angle of 53.8° against 59.1° for the film with untreated silica. However, the wettability loss rate of the materials remains unaffected by the presence of functionalized silica.
Effect of core–sheath bi‐polymeric scaffolds fabricated from acid‐soluble collagen and poly(lactic acid) derivatives on wound healing
Authors: Mukta Nasima Akter , Ahmed Samina , Sarwaruddin Chowdhury A. M. , Tareq Shafi M. , Sajib Abu Ashfaqur , Bashar M. S. , Haque Papia 
Published: May 2024

AbstractThe core–sheath bi‐polymeric scaffold has been proven as an encouraging material based on the requirement of scaffolds. This study aims to prepare electrospun core–sheath scaffolds by using acid‐soluble collagen (ASC) as core material and poly(lactic acid) (PLA) or PLA‐g‐VAc as sheath material to get the most in combination from a hydrophilic and a hydrophobic polymer. ASC is extracted from waste Tilapia fish skin conserving the triple helix structure of the α1 (130 kDa) chain, and a α2 (120 kDa) chain cross‐linked with the β (280 kDa) chain confirmed by amino acid profile, sodium dodecyl sulphate‐polyacrylamide gel electrophoresis. PLA‐g‐VAc is prepared by grafting vinyl acetate (VAc) onto the PLA chain using benzoyl peroxide as the initiator. FT‐IR, 1H NMR, and 13C NMR of PLA‐g‐VAc reveal that grafting occurs between the double bond of VAc and the methine group of PLA. The morphology of the scaffolds is determined by the field emission scanning electron microscope. FT‐IR, thermogravimetric analysis, differential scanning calorimetry, XRD, and water contact angle measurements are used for further characterization of scaffolds. In vivo, cytotoxicity analysis on the Vero cell line exposes that scaffolds are biocompatible. Application of scaffolds to the surgically produced wounding of skin in a rat model followed by histological assay indicates the enhanced properties of core–sheath scaffolds rather than the single polymeric scaffolds.
Engineering Rings in Network Materials
Authors: Neophytou Andreas , Chakrabarti Dwaipayan 
Published: May 2024

AbstractNetwork materials can be crystalline or amorphous solids, or even liquids, where typically directional interactions link the building blocks together, resulting in a physical representation of a mathematical object, called a graph or equivalently a network. Rings, which correspond to a cyclic path in the underlying network, consisting of a sequence of vertices and edges, are medium‐range structural motifs in the physical space. This Perspective presents an overview of recent studies, which showcase the importance of rings in the emergence of crystalline order as well as in phase transitions between two liquid phases for certain network materials, comprised of colloidal or molecular building blocks. These studies demonstrate how the selection of ring sizes can be exploited for programming self‐assembly of colloidal open crystals with an underlying network and elucidate rings as a vehicle for entanglement that distinguishes the two liquid phases of different densities involved in liquid–liquid phase transitions of network liquids with local tetrahedral order. In this context, an outlook is presented for engineering rings in network materials composed of colloidal and molecular building blocks, with implications also for metal‐organic frameworks, which have been extensively studied as porous crystals, but, more recently, as network‐forming liquids and glasses as well.
Observer‐based controller design for blood glucose regulation for type 1 diabetic patients with disturbance estimation: A backstepping approach
Authors: Homayounzade Mohamadreza 
Published: May 2024

AbstractIn this paper, an observer‐based nonlinear controller is proposed to regulate blood glucose concentration (BGC) in type 1 diabetes mellitus (T1DM). The considered virtual patient model is the extended Bergmann minimal model, which is augmented by a meal disturbance and adapted to represent the insulin–glucose homeostasis of T1DM. The backstepping (BS) technique is used to design a closed‐loop feedback controller. The proposed controller does not need to measure insulin, plasma concentrations, and external disturbances while improving control performance and robustness against uncertainty. Insulin concentrations and plasma levels are estimated using state observers and disturbance using a disturbance estimator. These estimations are used as feedback to the controller. The asymptotic stability of the observer‐based controller is proved using the Lyapunov theorem. Furthermore, it is proven that the system is bounded input–bounded output (BIBO) stable in the presence of uncertainties caused by uncertain parameters and external disturbances. For real situations, we consider only the BGC available for measurement, and in addition, inter‐ and intra‐patient variability of system parameters is considered. The results confirm that the proposed controller can asymptotically regulate BGC through appropriate injection of insulin under meal disturbance and
of variations in system parameters.
Simultaneous robust model predictive control and state estimation for nonlinear systems with state‐ and input‐dependent uncertainties
Authors: Badfar Farid , Safavi Ali Akbar 
Published: May 2024

AbstractThe convergence and stability of uncertain nonlinear systems is a challenging problem in the nonlinear control area. Besides, in many practical cases, all states are not measurable and are affected by measurement noise. Based on this motivation, the first objective of this paper is to design a novel output feedback robust model predictive control approach for nonlinear systems with state‐ and input‐dependent uncertainties and measurement noise. This approach combines state estimation and robust model predictive control (MPC) into one min–max optimization and by solving the optimization, these two tasks are performed simultaneously. The studied nonlinear system comprises a linear part, a nonlinear part, and a function that denotes the state‐ and input‐dependent uncertainties. Therefore, the other objective is to reduce the computational complexity; thus, the system's nonlinear term and the aforementioned uncertainties are converted into additional disturbances. Subsequently, the optimization problem becomes a quadratic form, which leads to global convergence with the appropriate selection of objective function weights. Besides, this paper explores the convergence of the closed‐loop system states and the sufficient synthesis conditions to guarantee input‐to‐state stability. The implementation on a numerical example and a CSTR process demonstrate the applicability and reliability of the proposed approach.
‘Sir, I don't know what I'm doing’: An investigation into the role of happy accidents in a secondary school art classroom
Authors: Marx Hugo 
Published: May 2024

AbstractThis research project explores the use of ‘happy accidents’ as agents for facilitating more meaningful and critical exploration in secondary school art. Owing to a preoccupation with standardisation and quantifiable results, the more nebulous and invisible qualities of art have become deprioritised within many curricula. This paradigm creates ‘safe’ pedagogies that place emphasis on verisimilitude and technical acme as the yardstick for ‘successful’ artwork, preserving the identity of teachers within the epistemological frameworks that dictate education. Equally, as competitive individualism and reward demarcate education, young people are spending more time partaking in activities for their instrumental value. This ‘teaching‐to‐test’ model translates to formalist, linear modes of making as the most expedient means of achieving grades. The following research aimed to trouble this status quo and offers a pedagogy that allows for more responsive, playful and personal approaches to experimental artmaking. The mechanism used as a springboard into inquiry was the ‘happy accident’, facilitated by the use of unpredictable media such as Photoshop and photocopying. Adopting a middle ground between Atkinson's ‘unknown’ and the inferentialist model described by Walton, students had the latitude to combine known and unknown knowledge to push their artmaking into more meaningful territory, whilst preserving evidence of the ‘mark scheme’. To bolster my attempts at disrupting canonised imagery of ‘good’ school art, students also troubled the common practice of creating overly embellished, illustrative sketchbooks, with the creation of self‐made, A2, portfolio style books. The knowledge produced in this project was interrogated within a multimodal, arts‐based research methodology: through interview analysis and the analysis of the artwork, or artefacts, produced.