bluuebunny/crossref_metadata_2025_split huggingface dataset:
Discovering a Single‐Atom Catalyst for CO2 Electroreduction to C1 Hydrocarbons: Thermodynamics and Kinetics on Aluminum‐Doped Copper
Authors: John Anwin , Verma Anand Mohan , Shaneeth M. , Govind Rajan Ananth 
Published: May 2023

AbstractThe electrochemical reduction of carbon dioxide (CO2) to hydrocarbons is a potential option to achieve carbon neutrality. Although copper (Cu) shows the highest activity for the CO2 reduction reaction (CO2RR) to hydrocarbons among metals, high reaction overpotentials and significant H2 production limit its use. We investigate single‐atom alloys (SAAs) of ten metals (Ag, Au, Fe, Ir, Ni, Pd, Pt, Rh, Ru, Al) on Cu(111), which is the most‐favored facet on Cu for methane production, using density functional theory. We examined the dopants’ ability to lower the free energy of the elementary reaction, *CO to *CHO, which is the potential‐determining step (PDS). Out of the SAAs studied, only Al‐doped Cu demonstrated a lowering of the PDS free energy. Additionally, weaker adsorption energies of *CO and *H on Al−Cu(111) suggest a preference for C1 hydrocarbons and inhibition of H2 evolution. Finally, activation barrier calculations for the PDS on Al−Cu(111) involving an explicitly hydrated proton indicated better intrinsic activity for C1 hydrocarbons compared to pure Cu(111). We also confirmed the stability of Al−Cu SAA compared to small Al clusters. Through a comprehensive study of both thermodynamics and kinetics, our study presents Al−Cu SAA as a promising catalyst for CO2 electroreduction to C1 hydrocarbons.
Enhancing CO2 Reduction Efficiency on Cobalt Phthalocyanine via Axial Ligation
Authors: Kang Hongxing , Staples‐West Aaliyah , Washington Audrey , Turchiano Chris , Cooksy Andrew , Huang Jier , Gu Jing 
Published: May 2023

AbstractElectrochemical reduction of carbon dioxide (CO2RR) to value‐added products is a promising strategy to alleviate the greenhouse gas effect. Molecular catalysts, such as cobalt (II) phthalocyanine (CoPc), are known to be efficient electrocatalysts that are capable of converting CO2 into carbon monoxide (CO). Herein, we report an axial modification strategy to enhance CoPc's CO2RR performance. After coordinating with axial ligands, the electron density of Co was depleted via π‐backbonding. This π‐backbonding weakened the Co‐CO bond, resulting in rapid desorption of CO. Also, the presence axial ligands elevated the Co dz2 orbital energy, resulting in a significantly enhanced CO selectivity, evidenced by an increased faradaic efficiency (FE) from 82 % (CoPc) to 91 % and 94 % with the presence of pyridine (CoPc‐py) and imidizal ligands (CoPc‐im), respectively, at −0.82 V vs. RHE. Density functional theory calculations reveal that axial ligation of CoPc can reduce the energy barrier for CO2 activation and facilitate the formation of *COOH.
First Example of 1,2,5‐Oxadiazole‐Based Hypergolic Ionic Liquids: A New Class of Potential Energetic Fuels
Authors: Shaferov Alexander V. , Arakelov Sergey T. , Teslenko Fedor E. , Pivkina Alla N. , Muravyev Nikita V. , Fershtat Leonid L. 
Published: May 2023

AbstractThe development of liquid energetic fuels with improved properties is an important topic in space propulsion technologies. In this manuscript, a series of energetic ionic liquids incorporating a 1,2,5‐oxadiazole ring and nitrate, dicyanamide or dinitramide anion was synthesized and their physicochemical properties were evaluated. The synthesized compounds were fully characterized and were found to have good thermal stabilities (up to 219 °C) and experimental densities (1.21–1.47 g cm−3). Advantageously, 1,2,5‐oxadiazole‐based ionic liquids have high combined nitrogen‐oxygen contents (up to 64.4 %), while their detonation velocities are on the level of known explosive TNT, and combustion performance exceeds those of benchmark 2‐hydroxyethylhydrazinium nitrate. Considering the established hypergolicity with H2O2 in the presence of a catalyst, and insensitivity to impact, synthesized ionic liquids have strong application potential as energetic fuels for space technologies.
Synthesis, Structural Characterization, and Bonding of Molecular Heavier Beryllium Chalcogenides
Authors: Czernetzki Corinna , Tröster Tobias , Endres Lukas , Endres Franziska , Arrowsmith Merle , Gärtner Annalena , Fantuzzi Felipe , Braunschweig Holger 
Published: May 2023

AbstractThe reactions of a cyclic alkyl(amino)carbene (CAAC)‐stabilized beryllium radical with E2Ph2 (E=S, Se, Te) and of a beryllole with HEPh (E=S, Se) yield the corresponding beryllium phenylchalcogenides, including the first structurally authenticated beryllium selenide and telluride complexes. Calculations show that their Be−E bonds are best described by the interaction between the Be+ and E− fragments, with Coulombic forces accounting for ca. 55 % of the attraction and orbital interactions dominated by the σ component.
Polyrotaxane‐Based Functional Materials Enabled by Molecular Mobility and Conformational Transition†
Authors: Cui Qinke , Zhang Xinxing 
Published: May 2023

Comprehensive SummarySlide‐ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications. There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes. However, most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles. In this review, we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications. Different designs of polyrotaxane‐based functional materials are presented to improve the potential for applications including self‐healing stretchable elastomers/gels, stimuli‐responsive smart devices, battery electrode binders, and biomedical drug delivery. It is anticipated that this review will provide insights and guidance for future developments in the design, synthesis and application of polyrotaxane‐based functional materials.
Photophysics of Glycosylated Ring‐Fused Chlorin Complexes and Their Photosensitizing Effects on Cancer Cells
Authors: Hageberg Ingvild U. , Arja Katrianne , Vindstad Benedikte E. , Bergvoll Johannes K. , Gederaas Odrun A. , Melø Thor‐Bernt , Nilsson K. Peter R. , Lindgren Mikael 
Published: May 2023

AbstractThe future of photodynamic therapy (PDT) as a promising cancer treatment relies on the development of new selective and effective photosensitizers (PS) with improved photophysical and biochemical qualities. Herein, we present the synthetic procedure, photophysical properties and photosensitizing effects of novel glycosylated 4,5,6,7‐tetrahydropyrazolo[1,5‐a]pyridine] fused chlorin agents featuring either glucose, galactose, or N‐acetyl glucosamine. It is shown that both the proto‐ and Zn2+‐ion forms of the ring‐stabilized glycochlorins exhibit the required photophysical properties in terms of triplet excited states and singlet oxygen generation, the latter more than 50 % in organic solvents such as CHCl3. Employing the rat AY‐27 and human T24 cancer cell models, it was found that these are superior to the corresponding unglycosylated chlorin in biological activity, and moreover, the proto form is 2–3 times superior to the Zn‐stabilized variant. Provisional flow cytometry and cell localization studies of the proto‐form indicate both necrotic and apoptotic biological activity, and that the photosensitizer localizes in the mitochondria, cell membrane and lysosomes. However, the localization into the lysosomes is dominating and increases substantially with time. We anticipate the findings will aid in the development of photosensitizers for targeted cancer PDT.
Portfolio performance implications of investment in renewable energy equities: Green versus gray
Authors: Lean Hooi Hooi , Pizzutilo Fabio , Gleason Kimberly 
Published: May 2023

AbstractThe Sustainable Development Goals of the United Nation and interest by investors in Environmental, Social and Governance (ESG) investment strategies have caused a rapid shift to the green or renewable energy sector, from traditional or gray (oil, gas, and coal) energy companies. In this study, we examine whether and to what extent, financially speaking, there is a price to pay for investing in renewable energy sector equity. Moreover, we seek to determine whether green investments can be considered a hedge during times of financial stress. We find that alphas from investments in a portfolio of gray (overall energy sector) stocks and versus a portfolio of renewable energy equities during an exogenous, non‐financial shock—the COVID‐19 pandemic—and during non‐crisis periods did not differ statistically. However, the renewable energy index showed higher idiosyncratic volatility than the energy index, as expected. The results are robust to alternative model specifications. From a practical perspective, our results are informative in that they provide insights into the tradeoffs associated with renewable energy investments. In particular, risk‐adjusted returns to a renewable energy portfolio may be affected by greater idiosyncratic risk.
Circulating CXCR5+ natural killer cells are expanded in patients with myasthenia gravis
Authors: Ge Meng‐Ru , Yang Chun‐Lin , Li Tao , Du Tong , Zhang Peng , Li Xiao‐Li , Dou Ying‐Chun , Duan Rui‐Sheng 
Published: May 2023

AbstractObjectivesMyasthenia gravis (MG) is a classic autoantibody‐mediated disease in which pathogenic antibodies target postsynaptic membrane components, causing fluctuating skeletal muscle weakness and fatigue. Natural killer (NK) cells are heterogeneous lymphocytes that have gained increasing attention owing to their potential roles in autoimmune disorders. This study will investigate the relationship between the distinct NK cell subsets and MG pathogenesis.MethodsA total of 33 MG patients and 19 healthy controls were enrolled in the present study. Circulating NK cells, their subtypes and follicular helper T cells were analysed by flow cytometry. Serum acetylcholine receptor (AChR) antibody levels were determined by ELISA. The role of NK cells in the regulation of B cells was verified using a co‐culture assay.ResultsMyasthenia gravis patients with acute exacerbations had a reduced number of total NK cells, CD56dim NK cells and IFN‐γ‐secreting NK cells in the peripheral blood, while CXCR5+ NK cells were significantly elevated. CXCR5+ NK cells expressed a higher level of ICOS and PD‐1 and a lower level of IFN‐γ than those in CXCR5− NK cells and were positively correlated with Tfh cell and AChR antibody levels. In vitro experiments demonstrated that NK cells suppressed plasmablast differentiation while promoting CD80 and PD‐L1 expression on B cells in an IFN‐γ‐dependent manner. Furthermore, CXCR5− NK cells inhibited plasmablast differentiation, while CXCR5+ NK cells could more efficiently promote B cell proliferation.ConclusionThese results reveal that CXCR5+ NK cells exhibit distinct phenotypes and functions compared with CXCR5− NK cells and might participate in the pathogenesis of MG.
High resolution lidar data shed light on inter‐island translocation of endangered bird species in the Hawaiian Islands
Authors: Gallerani Erica M. , Burgett Jeff , Vaughn Nicholas , Berio Fortini Lucas , Fricker Geoffrey Andrew , Mounce Hanna , Gillespie Thomas W. , Crampton Lisa , Knapp David , Hite Justin M. , Gilb Roy 
Published: May 2023

AbstractTranslocation, often a management solution reserved for at‐risk species, is a highly time‐sensitive intervention in the face of a rapidly changing climate. The definition of abiotic and biotic habitat requirements is essential to the selection of appropriate release sites in novel environments. However, field‐based approaches to gathering this information are often too time intensive, especially in areas of complex topography where common, coarse‐scale climate models lack essential details. We apply a fine‐scale remote sensing‐based approach to study the 'akikiki (Oreomystis bairdi) and 'akeke'e (Loxops caeruleirostris), Hawaiian honeycreepers endemic to Kaua'i that are experiencing large‐scale population declines due to warming‐induced spread of invasive disease. We use habitat suitability modeling based on fine‐scale light detection and ranging (lidar)‐derived habitat structure metrics to refine coarse climate ranges for these species in candidate translocation areas on Maui. We found that canopy density was consistently the most important variable in defining habitat suitability for the two Kaua'i species. Our models also corroborated known habitat preferences and behavioral information for these species that are essential for informing translocation. We estimated a nesting habitat that will persist under future climate conditions on east Maui of 23.43 km2 for 'akikiki, compared to the current Kaua'i range of 13.09 km2. In contrast, the novel nesting range for 'akeke'e in east Maui was smaller than its current range on Kaua'i (26.29 vs. 38.48 km2, respectively). We were also able to assess detailed novel competitive interactions at a fine scale using models of three endemic Maui species of conservation concern: 'ākohekohe (Palmeria dolei), Maui 'alauahio (Paroreomyza montana), and kiwikiu (Pseudonestor xanthophrys). Weighted overlap areas between the species from both islands were moderate (<12 km2), and correlations between Maui and Kaua'i bird habitat were generally low, indicating limited potential for competition. Results indicate that translocation to east Maui could be a viable option for 'akikiki but would be more uncertain for 'akeke'e. Our novel multifaceted approach allows for the timely analysis of both climate and vegetation structure at informative scales for the effective selection of appropriate translocation sites for at‐risk species.
Time‐of‐day and day‐of‐week patterns of binge eating and relevant psychological vulnerabilities in binge‐eating disorder
Authors: Forester Glen , Schaefer Lauren M. , Dodd Dorian R. , Burr Emily K. , Bartholomay Julia , Berner Laura A. , Crosby Ross D. , Peterson Carol B. , Crow Scott J. , Engel Scott G. , Wonderlich Stephen A. 
Published: May 2023

AbstractObjectiveThe present study sought to characterize the temporal patterns of binge eating and theorized maintenance factors among individuals with binge‐eating disorder (BED).MethodEcological momentary assessment of 112 individuals and mixed‐effects models were used to characterize the within‐ and between‐day temporal patterns of eating behaviors (binge eating, loss of control only eating, and overeating only), positive and negative affect, emotion regulation difficulty, and food craving.ResultsRisk for binge eating and overeating only was highest around 5:30 p.m., with additional binge‐eating peaks around 12:30 and 11:00 p.m. In contrast, loss of control eating without overeating was more likely to occur before 2:00 p.m. Risk for binge eating, loss of control only eating, and overeating only did not vary across days in the week. There was no consistent pattern of change in negative affect throughout the day, but it decreased slightly on the weekend. Positive affect showed a decrease in the evenings and a smaller decrease on the weekend. The within‐day patterns of food craving, and to some extent emotion regulation difficulty, resembled the pattern of binge eating, with peaks around meal times and at the end of the night.DiscussionIndividuals with BED appear most susceptible to binge‐eating around dinner time, with heightened risk also observed around lunch time and late evening, though the effects were generally small. These patterns appear to most strongly mimic fluctuations in craving and emotion dysregulation, although future research is needed to test the temporal relationships between these experiences directly.Public SignificanceIt is unknown which times of the day and days of the week individuals with binge‐eating disorder are most at risk for binge eating. By assessing binge‐eating behaviors in the natural environment across the week, we found that individuals are most likely to binge in the evening, which corresponds to the times when they experience the strongest food craving and difficulty with regulating emotions.
Coronary revascularization for heart failure with coronary artery disease: A systematic review and meta‐analysis of randomized trials
Authors: Iaconelli Antonio , Pellicori Pierpaolo , Dolce Pasquale , Busti Matteo , Ruggio Aureliano , Aspromonte Nadia , D'Amario Domenico , Galli Mattia , Princi Giuseppe , Caiazzo Elisabetta , Rezig Asma O.M. , Maffia Pasquale , Pecorini Giovanni , Crea Filippo , Cleland John G.F. 
Published: May 2023

AimsCoronary artery disease (CAD) is a common cause of heart failure (HF). Whether coronary revascularization improves outcomes in patients with HF receiving guideline‐recommended pharmacological therapy (GRPT) remains uncertain; therefore, we conducted a systematic review and meta‐analysis of relevant randomized controlled trials (RCTs).Methods and resultsWe searched in public databases for RCTs published between 1 January 2001 and 22 November 2022, investigating the effects of coronary revascularization on morbidity and mortality in patients with chronic HF due to CAD. All‐cause mortality was the primary outcome. We included five RCTs that enrolled, altogether, 2842 patients (most aged <65 years; 85% men; 67% with left ventricular ejection fraction ≤35%). Overall, compared to medical therapy alone, coronary revascularization was associated with a lower risk of all‐cause mortality (hazard ratio [HR] 0.88, 95% confidence interval [CI] 0.79–0.99; p = 0.0278) and cardiovascular mortality (HR 0.80, 95% CI 0.70–0.93; p = 0.0024) but not the composite of hospitalization for HF or all‐cause mortality (HR 0.87, 95% CI 0.74–1.01; p = 0.0728). There were insufficient data to show whether the effects of coronary artery bypass graft surgery or percutaneous coronary intervention were similar or differed.ConclusionsFor patients with chronic HF and CAD enrolled in RCTs, the effect of coronary revascularization on all‐cause mortality was statistically significant but neither substantial (HR 0.88) nor robust (upper 95% CI close to 1.0). RCTs were not blinded, which may bias reporting of the cause‐specific reasons for hospitalization and mortality. Further trials are required to determine which patients with HF and CAD obtain a substantial benefit from coronary revascularization by either coronary artery bypass graft surgery or percutaneous coronary intervention.
Magnetic Anisotropy Transfer from Mono‐ to Polymetallic Complexes
Authors: Poncet Marion , Li Ang , Gontard Geoffrey , Chamoreau Lise‐Marie , Li Yanling , Lisnard Laurent , Von Bardeleben Jurgen , Dey Sourav , Rajaraman Gopalan , Journaux Yves 
Published: May 2023

AbstractThe reaction of multi‐bidentate oxamate‐based copper(II) complexes with the [Ni(iPrtacn)Cl2] complex (iPrtacn:1,4,7‐triisopropyl‐1,4,7‐triazacyclononane) has been investigated. X‐ray diffraction studies reveal that for all compounds the oxamato κO,κΟ’ bidentate coordination site replaces the two chloride ions in [Ni(iPrtacn)Cl2] to form trimetallic {CuNi2} (1–3), hexametallic {Cu2Ni4} (4) and enneametallic {Cu3Ni6} (5) complexes. The investigation of the magnetic properties shows that Cu−Ni interactions through the oxamato bridge are in the expected range (−111 cm−1, −68 cm−1). For 1–3, both the sign and strength of the magnetic couplings are computed independently from DFT calculations, and these estimates broadly agree with the experiments. The magnetization measurements and EPR studies reveal that 1–3 are anisotropic: a significant portion of the large anisotropy of the [Ni(iPrtacn)Cl2] complex is retained, resulting in a D value for the S=3/2 ground state of 5 cm−1 on average. This is no longer the case for 4 and 5 where the anisotropy of the Ni(II) complexes is diluted due to the high nuclearity of the final edifices. These results show that it is possible to obtain trimetallic complexes with a high anisotropy and a high spin value for the ground state by a judicious choice of the interacting metal ions.
Asymmetric Synthesis of Monofluorinated Carbocyclic Alcohols and Vicinal Difluorinated Heterocycles and Carbocycles
Authors: Bacheley Lucas , Molina Betancourt Ricardo , Ravindra Rathies , Guillamot Gérard , Phansavath Phannarath , Ratovelomanana‐Vidal Virginie 
Published: May 2023

AbstractA straightforward method to access novel families of enantioenriched cis‐monofluorinated carbocyclic alcohols has been developed through ATH/DKR in up to 97 % yield, up to 99 : 1 dr and enantioinductions up to 97 % ee. Trans‐difluorinated indans, tetrahydronaphthalenes, tetrahydroquinolines and chromans have been synthesized as well by deoxofluorination of the corresponding cis‐fluoro alcohols. The reaction was performed on a series of variously substituted 3‐fluorochromanols, 3‐fluorotetrahydroquinolinols, 2‐fluoro inden‐1‐ols and 2‐fluoro 1,2,3,4‐tetrahydronaphthalen‐1‐ols in up to 86 % yields, with diastereoselectivities up to 97 : 3 and enantioselectivities up to >99 % ee.
Early executive control buffers risk for adolescent psychopathology during the COVID‐19 pandemic
Authors: Laifer Lauren M. , Tomaso Cara C. , Chang Olivia D. , Phillips Eric M. , James Tiffany D. , Nelson Jennifer Mize , Espy Kimberly Andrews , Alex Mason W. , Nelson Timothy D. 
Published: May 2023

AbstractBackgroundThe coronavirus disease 2019 (COVID‐19) pandemic has had a global impact on youth mental health, and there is a critical need for research examining individual factors that contribute to increased psychopathology during the pandemic. The current study explored whether executive control (EC) abilities in early childhood interact with COVID‐related stress to attenuate risk for adolescent psychopathology during the first 6 months of the pandemic.MethodsParticipants were 337 youth (49% female) living in a small midwestern city in the United States. Participants completed EC tasks when they were approximately 4.5 years old as part of a longitudinal study investigating cognitive development. At annual laboratory visits during adolescence and before the pandemic, participants (Mage = 14.57) reported on mental health symptoms. In July and August of 2020, participants (Mage = 16.57) reported on COVID‐related stress and depression, anxiety, and trauma symptoms.ResultsCOVID‐related stress was associated with increased internalizing problems after controlling for prepandemic symptom levels. Further, the impact of COVID‐related stress on adolescent internalizing problems was moderated by preschool EC, with higher levels of EC buffering the effects of COVID‐related stress on adolescent internalizing problems.ConclusionsFindings highlight the importance of promoting EC early in development, as well as screening for EC deficits and implementing targeted intervention strategies across the lifespan to help reduce the impact of stress on adolescent internalizing problems.