bluuebunny/crossref_metadata_2025_split huggingface dataset:
Identification of glycosylated nucleosides in small synthetic glyco‐RNAs
Authors: Michael Frank St. , Hamouda Maha Ben , Stupak Jacek , Li Jianjun , Pearson Angela , Sauvageau Janelle 
Published: December 2023

AbstractRecently, the post‐transcriptional modification of RNA with N‐glycans was reported, changing the paradigm that RNAs are not commonly N‐glycosylated. Moreover, glycan modifications of RNA are investigated for therapeutic targeting purposes. But the glyco‐RNA field is in its infancy with many challenges to overcome. One question is how to accurately characterize glycosylated RNA constructs. Thus, we generated glycosylated forms of Y5 RNA mimics, a short non‐coding RNA. The simple glycans lactose and sialyllactose were attached to the RNA backbone using azide‐alkyne cycloadditions. Using nuclease digestion followed by LC−MS, we confirmed the presence of the glycosylated nucleosides, and characterized the chemical linkage. Next, we probed if glycosylation would affect the cellular response to Y5 RNA. We treated human foreskin fibroblasts in culture with the generated compounds. Key transcripts in the innate immune response were quantified by RT‐qPCR. We found that under our experimental conditions, exposure of cells to the Y5 RNA did not trigger an interferon response, and glycosylation of this RNA did not have an impact. Thus, we have identified a successful approach to chemically characterize synthetic glyco‐RNAs, which will be critical for further studies to elucidate how the presence of complex glycans on RNA affects the cellular response.
Intranodal lymphangiography with lipiodol as a diagnostic and therapeutic approach for spontaneous cervical chyle leak
Authors: Sasaki Yuki , Sakuhara Yusuke , Sasaki Satoru , Maeda Taku , Yamamoto Yuhei , Ishikawa Kosuke 
Published: December 2023

Key Clinical MessageWe present a case of spontaneous cervical chyle leak that showed as left‐sided neck swelling. Spontaneous chyle leak is extremely rare. Lymphangiography with lipiodol is useful as a diagnostic and therapeutic approach for chyle leak.
Insights into the Structural Evolution Process of Na/ZnFe2O4 Spinel Catalyst in CO2 Hydrogenation
Authors: Gong Xiaoqian , Liu Yi , He Ruonan , Xu Xiaoying , Han Zhihua , Chen Jingyun , Feng Bo , Wang Zhou‐jun , Xing Aihua 
Published: December 2023

AbstractThe CO2 hydrogenation to olefins process over Fe‐based catalysts offer a promising route for the production of high‐value chemicals from non‐fossil route. Herein, we present a Na promoted ZnFe2O4 spinel catalyst and their structural evolution from fresh state to reduction and to reaction period was elucidated. The clear phase segregation between Fe and Zn occurred after reduction/reaction because of crystalline phase transformation in the order of ZnFe2O4→ZnO+Fe7C3+χ‐Fe5C2→FeO+ZnO+Fe7C3+χ‐Fe5C2. The formation of iron carbide phases (Fe7C3 and χ‐Fe5C2) was enhanced dramatically by Na promoter. The adjacent Na promoter increase the electron density in Fe−Zn interfaces and enhance its ability to dissociate CO* to form adsorbed CHx* species, thus promoting the formation of olefins. This Na promoted rich electronic Fe−Zn interfaces alters the balance between iron oxides and iron carbides on the catalyst surface, which accelerate the chain growth reaction and facilitate the coupling efficiency of tandem reaction. The various catalysts were characterized by N2 physisorption, SEM, HR‐TEM, HAADF‐STEM, ex‐situ /in situ XRD, Mössbauer spectra, ICP, in situ XPS, and operando DRIFTs.
Tuning Strong Metal‐Support Interactions for Enhancing Direct Deoxygenation of Biomass‐Lignin Derived Phenolics
Authors: Ding Shining , Zhu Xinli 
Published: December 2023

AbstractCatalytic direct deoxygenation (DDO) of phenolic compounds to aromatics is an appealing approach for utilization of biomass‐lignin with minimal amount of H2 consumption. Metal/reducible metal oxide catalysts provide two functionalities, i. e., C−H bond formation (hydrogenation) and C−O bond breakage (deoxygenation), required for this reaction that takes place at the interfacial perimeter sites. Strong metal‐support interactions (SMSI) can profoundly alter the density and property of such sites. This short review summarized recent advances in tuning SMSI for enhancing DDO of phenolics. The approaches of varying reduction temperature, modulation of crystal facets and crystal phases of metal oxide, and reduction of mixed metal oxide were discussed for the origin for formation of SMSI, the degree of SMSI, and its consequence on the DDO performance. The analysis revealed that intermediate degree of SMSI with maximal density of metal/oxide interfacial perimeter site enhances DDO while minimizing unfavorable side reactions. This short review highlights the concept of tuning the interfacial perimeter sites via SMSI for reactions which require multiple functionalities and take place at the metal/oxide interface.
School counseling practices related to postsecondary STEM participation
Authors: Gearns Richard , Kelly Angela M. , Bugallo Mónica F. 
Published: December 2023

AbstractThis qualitative exploratory cross‐case analysis analyzed the beliefs and practices of high school counselors related to science, technology, engineering, and mathematics (STEM) academic advisement, postsecondary planning, and career participation. Interviews were conducted with high school counselors (N = 13) who were purposively sampled to represent a diversity of schools in terms of demographic variables. Findings indicated that high school counselors perceived that (a) sociocultural factors influenced student preparation for STEM, career planning, and decision making; (b) students’ STEM‐related career goals and academic behaviors were sometimes misaligned, and academic advisement often mediated this tension; and (c) their professional STEM knowledge, beliefs, and practices were influenced by professional preparation, workplace characteristics, and their academic experiences. Implications include the need for early, sustained high school STEM counseling and academic advisement; accessible professional development in STEM preparation and careers to promote multiple pathways and reduce school counselor bias; and encouraging family involvement in STEM career decision making.
A Review of the Recent Advances in Development of Noble Metal‐Free Materials as Electrocatalysts for Hydrogen and Oxygen Evolution Reactions
Authors: Farajzadeh Mustafa , Rahsepar Fatemeh Rahnemaye 
Published: December 2023

AbstractSustainable energy development can no longer be met by fossil fuels alone. Hence, electrochemical water splitting containing oxygen and hydrogen evolution reactions is appealing as a clean energy pathway. As respects the water splitting efficiency which is largely determined by the selectivity, durability, and intrinsic activity of the electrocatalysts, one of the most challenging questions when studying these materials is “which category of electrocatalysts will show the best performance in this issue?” The best electrocatalysts for water splitting still come from noble metals. Although these materials show particularly good efficiency, but due to the scarce resources their massive use is limited. Therefore, the noble metal‐free materials due to their stability, efficiency, abundance and variety of reaction sites were introduced as an interesting candidate for electrochemical water splitting reactions. In this review, based on the important above‐mentioned points, our attention was focused on key categories based on transition metals (TMs), metal organic framework derived (MOF‐derived), carbon‐based hybrids, graphitic carbon nitride (g‐C3N4) hybrids, and bio‐assisted electrocatalysts. These compounds have shown significant activity and stability for broad electrocatalysis applications in water splitting reactions and displaying remarkable potential to replace with noble metal‐based catalysts. This comprehensive review identifies rational strategies for designing and synthesizing high‐performance novel noble metal‐free electrocatalysts for water splitting.
Organometallic Bridge Diversification of Bicyclo[1.1.1]pentanes
Authors: Anderson Joseph M. , Poole Darren L. , Cook Gemma C. , Murphy John A. , Measom Nicholas D. 
Published: December 2023

AbstractBicyclo[1.1.1]pentane (BCP) derivatives have attracted significant recent interest in drug discovery as alkyne, tert‐butyl and arene bioisosteres, where their incorporation is frequently associated with increased compound solubility and metabolic stability. While strategies for functionalisation of the bridgehead (1,3) positions are extensively developed, platforms allowing divergent substitution at the bridge (2,4,5) positions remain limited. Recent reports have introduced 1‐electron strategies for arylation and incorporation of a small range of other substituents, but are limited in terms of scope, yields or practical complexity. Herein, we show the synthesis of diverse 1,2,3‐trifunctionalised BCPs through lithium‐halogen exchange of a readily accessible BCP bromide. When coupled with medicinally relevant product derivatisations, our developed 2‐electron “late stage” approach provides rapid and straightforward access to unprecedented BCP structural diversity (>20 hitherto‐unknown motifs reported). Additionally, we describe a method for the synthesis of enantioenriched “chiral‐at‐BCP” bicyclo[1.1.1]pentanes through a novel stereoselective bridgehead desymmetrisation.
A green approach for cohesive recycling and regeneration of electrode active materials from spent lithium‐ion batteries
Authors: Vinayak Anil Kumar , Wang Xiaolei 
Published: December 2023

AbstractThe implementation of the green energy transition by reducing reliance on fossil fuels has fueled the burgeoning demand for lithium‐ion batteries in grid‐level energy storage systems and electric vehicles. The growth of portable electronic devices has also contributed to this exponential demand, creating both logistical and environmental challenges in the supply of raw materials such as lithium and the management of end‐of‐life batteries. Current recycling methods for spent batteries are both energy‐intensive and inefficient. To address these issues, a green approach using organic acid mixtures has been proposed to reclaim lithium from spent cathodes and recover and purify graphite from spent anodes, while also regenerating its structure. The effectiveness of this method is demonstrated through the use of organic acid mixtures to leach and reclaim lithium from NCM 622 batteries. On the anode side, a curing–leaching strategy using organic acids is employed to purify spent graphite, which is subsequently calcined to enhance its interlayer structure conducive to better intercalation of Li+ and improve electrochemical performance. Additionally, recovered graphite is tailored with carbon using water bath carbonization to repair structural defects caused by lithium intercalation and improve electrochemical performance while augmenting the regenerated graphite's quality, equipping it to be reused in batteries or upcycled applications.
Controlling Three‐Step and Five‐Step Spin Transitions by Polymorphism in an FeIII Spin Crossover Complex
Authors: Wu Yingying , Peng Shuang , Zhang Ziyi , Gao Yue , Xu Guangyan , Dai Jingwei , Li Zhao‐Yang , Yamashita Masahiro 
Published: December 2023

Comprehensive SummaryRegulating spin crossover (SCO) behavior, especially controlling the spin transition steps, is an important scientific issue, mainly because people aim to control spin bistability and multistability. Presently, SCO bistability can be regulated by changing the ligand‐modifying species, non‐coordinated anions, guest molecules, and metal‐ion dopant. However, the control of multistability is extremely challenging, especially in Fe(III) SCO compounds. Here, we report that [FeIII(H‐5‐Br‐thsa)(5‐Br‐thsa)]·H2O (5‐Br‐thsa = (5‐bromo‐2‐hydroxybenzylidene)hydrazinecarbothioamide), a compound we have reported before, exists in two polymorphic forms: polymorph 1 exhibits three‐step SCO, and polymorph 2 shows five‐step SCO, with multi‐step SCO behavior effectively regulated by polymorphism. According to single‐crystal and powder X‐ray diffractometry, polymorphs 1 and 2 crystallize in different space groups during their spin transitions, with two‐step symmetry breaking observed (Pbcn → Pnc2 → Pbcn for polymorph 1; P21/n → Pn → P21/n for polymorph 2). We realized that the behavior of these two polymorphs depends significantly on the structure, including (i) the average Fe—N bond distance, (ii) deformation of octahedral FeIII atoms, and (iii) distinct crystal packing, which account for the large differences observed in magnetic properties.
Satisfaction with care, general health, and mental health among sexual and gender minority cancer survivors: Results of the OUT National Cancer Survey
Authors: Kamen Charles S. , Gada Umang , Lyerly Reece , Scout N. F. N. 
Published: December 2023

AbstractBackgroundFew studies have attempted to characterize the cancer care experiences and outcomes of sexual and gender minority (SGM) patients with cancer, despite indications that this population experiences disparities across the cancer continuum. The current study used descriptive and exploratory methods to assess factors related to SGM cancer patients’ satisfaction with cancer care and self‐reported physical and mental health.MethodsThe authors designed a cross‐sectional self‐report online survey and recruited 3750 SGM cancer patient participants (mixed cancers; 85.6% White; 57% gay, 24% lesbian, 6.7% bisexual, and 6.2% transgender/gender nonbinary) using social media posts, partner organizations, and paid advertisements. They analyzed data using descriptive approaches and exploratory multivariate logistic regression models.ResultsOverall, 70.6% of participants reported feeling satisfied with the cancer care they received, 70% rated their physical health as very good or excellent, and 46% reported experiencing less than 5 days of poor mental health in the last month. In models including all participants, complete cases, and Black, Indigenous, and people of color (BIPOC), satisfaction with care was consistently associated with receiving treatment in an SGM welcoming environment. Physical health was consistently associated with having strong social support after cancer. Mental health was consistently associated with feeling safe disclosing SGM identities.ConclusionsSGM cancer patients treated in SGM‐welcoming environments were over six times more likely to be satisfied with the care they received than those treated in nonwelcoming environments; this and other modifiable factors could be the target of further study and intervention.
Improvement in left atrial strain following ferric carboxymaltose in heart failure: an analysis of the Myocardial‐IRON trial
Authors: Santas Enrique , del Canto Irene , Cardells Ingrid , Miñana Gema , Llàcer Pau , Almenar Luis , Fácila Lorenzo , Maceira Alicia M. , Sanchis Juan , Núñez Julio ,   Myocardial‐IRON Investigators
Published: December 2023

AbstractAimsIron deficiency (ID) is associated with an impaired cardiac function and remodelling in heart failure (HF). Treatment with ferric carboxymaltose (FCM) has been showed recently to improve biventricular systolic function and ventricular strain parameters in patients with HF with reduced ejection fraction and ID, but there is no evidence on the benefit of FCM on the left atrium (LA). In this study, we aimed to evaluate the effect of FCM on LA longitudinal strain (LA‐LS).Methods and resultsThis is a post hoc subanalysis of a double‐blind, placebo‐controlled, randomized clinical trial that enrolled 53 ambulatory patients with HF, left ventricular ejection fraction (LVEF) < 50%, and ID [Myocardial‐IRON trial (NCT03398681)], treated with FCM or placebo. Cardiac magnetic resonance‐featured tracking (CMR‐FT) strain changes were evaluated before and 7 and 30 days after randomization using linear mixed regression analysis. The median age of the sample was 68 years (interquartile range: 64–76), and 20 (69%) were men. Mean ± standard deviation of LVEF was 39 ± 11%, and most (97%) were in stable New York Heart Association class II. At baseline, mean LA‐LS was −8.9 ± 3.5%. At 30 days, and compared with placebo, LA‐LS significantly improved in those allocated to FCM treatment arm (LA‐LS = −12.0 ± 0.5 and −8.5 ± 0.6, respectively; −
3.55%, P < 0.001).ConclusionsIn patients with stable HF, LVEF < 50%, and ID, treatment with FCM was associated with short‐term improvements in LA‐LS assessed by CMR‐FT. Future works should assess the potential benefit of iron repletion on LA function.
Geriatric Nutritional Risk Index predicts bleeding event in patients with heart failure
Authors: Sato Yu , Yoshihisa Akiomi , Nozaki Yuji , Ohara Himika , Sugawara Yukiko , Abe Satoshi , Misaka Tomofumi , Sato Takamasa , Oikawa Masayoshi , Kobayashi Atsushi , Yamaki Takayoshi , Nakazato Kazuhiko , Takeishi Yasuchika 
Published: December 2023

AbstractAimsWe aimed to elucidate the association between malnutrition and the occurrence of bleeding events in patients with heart failure.Methods and resultsWe evaluated the nutritional status of patients with heart failure [n = 2044, median (inter‐quartile range) age 69.0 (59.0–78.0) years, 1209 (59.1%) males] using the Geriatric Nutritional Risk Index (GNRI). The primary endpoint was a composite of bleeding events such as haemorrhagic stroke or gastrointestinal bleeding. According to the survival classification and regression tree analysis, the accurate cut‐off point of GNRI for predicting the primary endpoint was 106.2. We divided the patients into two groups based on GNRI levels: high GNRI group (GNRI ≥ 106.2, n = 606, 29.6%) and low GNRI group (GNRI < 106.2, n = 1438, 70.4%). We compared the patients' characteristics and prognosis between the two groups. The low GNRI group was older [72.0 (63.0–79.0) vs. 63.0 (53.0–73.0) years, P < 0.001] and had a lower prevalence of male sex (56.9% vs. 64.5%, P = 0.001). There were no differences in the use of antiplatelet agents and anticoagulants between the two groups. Levels of B‐type natriuretic peptide were higher [321.1 (123.3–667.4) vs. 111.6 (42.6–235.4) pg/mL, P < 0.001] and levels of haemoglobin were lower [12.4 (10.8–13.7) vs. 14.2 (12.9–15.4) g/dL, P < 0.001] in the low GNRI group. The Kaplan–Meier analysis demonstrated that bleeding event rates were higher in the low GNRI group (log‐rank P < 0.001). The multivariable Cox proportional hazard analysis revealed that low GNRI (hazard ratio 1.952, 95% confidence interval 1.002–3.805, P = 0.049) was associated with bleeding events.ConclusionsHeart failure patients with poor nutritional status, determined by GNRI under 106.2, experienced high bleeding event rates. Comprehensive management is required to avoid bleeding event in those populations.
Reaction Pathway for the Aerobic Oxidation of Phosphines Catalyzed by Oxomolybdenum Salen Complexes
Authors: Rusmore Theo A. , Lander Chance , Nicholas Kenneth M. 
Published: December 2023

AbstractCatalysis of O‐atom transfer (OAT) reactions is a characteristic of both natural (enzymatic) and synthetic molybdenum‐oxo and ‐peroxo complexes. These reactions can employ a variety of terminal oxidants, e. g. DMSO, N‐oxides, and peroxides, etc., but rarely molecular oxygen. Here we demonstrate the ability of a set of Schiff‐base‐MoO2 complexes (cy‐salen)MoO2 (cy‐salen=N,N’‐cyclohexyl‐1,2‐bis‐salicylimine) to catalyze the aerobic oxidation of PPh3. We also report the results of a DFT computational investigation of the catalytic pathway, including the identification of energetically accessible intermediates and transition states, for the aerobic oxidation of PMe3. Starting from the dioxo species, (cy‐salen)Mo(VI)O2 (1), key reaction steps include: 1) associative addition of PMe3 to an oxo‐O to give LMo(IV)(O)(OPMe3) (2); 2) OPMe3 dissociation from 2 to produce mono‐oxo complex (cy‐salen)Mo(IV)O (3); 3) stepwise O2 association with 3 via superoxo species (cy‐salen)Mo(V)(O)(η1‐O2) (4) to form the oxo‐peroxo intermediate (cy‐salen)Mo(VI)(O)(η2‐O2) (5); 4) the O‐transfer reaction of PMe3 with oxo‐peroxo species 5 at the oxo‐group, rather than the peroxo unit leading, after OPMe3 dissociation, to a monoperoxo species, (cy‐salen)Mo(IV)(η2‐O2) (7); and 5) regeneration of the dioxo complex (cy‐salen)Mo(VI)O2 (1) from the monoperoxo triplet 37 or singlet 17 by a concerted, asynchronous electronic isomerization. An alternative pathway for recycling of the oxo‐peroxo species 5 to the dioxo‐Mo 1 via a bimetallic peroxo complex LMo(O)‐O−O‐Mo(O)L 8 is determined to be energetically viable, but is unlikely to be competitive with the primary pathway for aerobic phosphine oxidation catalyzed by 1.
AoI‐driven SWIPT‐enabled UAV trajectory optimization for two‐way relaying
Authors: Perera Tharindu D. Ponnimbaduge , Jayakody Dushantha Nalin K. 
Published: December 2023

AbstractMotivated by the timely need for fresh updates in time‐critical applications, this paper investigates the AoI‐driven UAV trajectory optimization for a two‐way relay network. The non‐linear simultaneous wireless information and power transfer (SWIPT) power‐splitting (PS) technique is used to provide the energy required for UAV communication considering hardware impairments. Amalgamating derived outage probability, AoI expression is obtained to evaluate data timeliness and its performance trade‐offs. Then, we optimize the trajectory of the UAV while minimizing the AoI performance within the given discretized time slot. The impact of the system parameters, that is, size of the status update, PS factor, outage probability, and UAV's position, on the AoI performance are extensively investigated.
Annual yields of multispecies grassland mesocosms outperformed monocultures across a drought gradient due to complementarity effects and rapid recovery
Authors: Haughey Eamon , McElwain Jennifer C. , Finn John A. 
Published: December 2023

AbstractBackgroundMore frequent and severe drought events due to climate change pose a major challenge for sustainable forage production in managed grasslands. This study investigated whether multispecies grassland communities can provide greater resistance to and/or recovery from drought compared to monoculture communities.MethodsMesocosms of Lolium perenne L., Cichorium intybus L., Trifolium repens L. and Trifolium pratense L. were established as monocultures, and a four‐species mixture. A drought gradient with five levels of water supply ranging from a mild to a severe treatment was applied for 10 weeks, in each of 2 years. Shoot biomass was harvested to assess drought resistance, drought recovery and annual yields. Root mass density and specific root length were measured in Year 2.ResultsAcross the drought gradient, four‐species communities had significantly larger annual yields than each of the four monocultures, indicating transgressive overyielding. This was despite relatively low drought resistance for four‐species communities compared with L. perenne and C. intybus monocultures. Recovery of yields following drought was high for all communities.ConclusionsMultispecies swards with complementary traits can provide a viable adaptation option across a wide range of drought severities. Application of a stress gradient methodology allowed a more detailed understanding of stress responses.