bluuebunny/crossref_metadata_2025_split huggingface dataset:
50 Years of Organoselenium Chemistry, Biochemistry and Reactivity: Mechanistic Understanding, Successful and Controversial Stories
Authors: Madabeni Andrea , Bortoli Marco , Nogara Pablo A. , Ribaudo Giovanni , Dalla Tiezza Marco , Flohé Leopold , Rocha João B. T. , Orian Laura 
Published: September 2024

AbstractIn 1973, two major discoveries changed the face of selenium chemistry: the identification of the first mammal selenoenzyme, glutathione peroxidase 1, and the discovery of the synthetic utility of the so‐called selenoxide elimination. While the chemical mechanism behind the catalytic activity of glutathione peroxidases appears to be mostly unveiled, little is known about the mechanisms of other selenoproteins and, for some of them, even the function lies in the dark. In chemistry, the capacity of organoselenides of catalyzing hydrogen peroxide activation for the practical manipulation of organic functional groups has been largely explored, and some mechanistic details have been clearly elucidated. As a paradox, despite the long‐standing experience in the field, the nature of the active oxidant in various reactions still remains matter of debate. While many successes characterize these fields, the pharmacological use of organoselenides still lacks any true application, and while some organoselenides were found to be non‐toxic and safe to use, to date no therapeutically approved use was granted. In this review, some fundamental and chronologically aligned topics spanning organoselenium biochemistry, chemistry and pharmacology are discussed, focusing on the current mechanistic picture describing their activity as either bioactive compounds or catalysts.
The erosion of rationality in high vulnerability conditions: A cognitive‐disruption perspective
Authors: Freling Traci , Saini Ritesh , Yang Zhiyong 
Published: September 2024

AbstractThis research examines how a decision‐maker's perceived vulnerability influences their susceptibility to the “anecdotal bias,” a phenomenon where statistical evidence is disregarded in favor of anecdotal information. Across six studies, our research shows that high vulnerability aggravates the anecdotal bias instead of reducing it. Study 1 provides preliminary evidence that high vulnerability exacerbates the anecdotal bias among individuals seeking decision‐relevant information in the context of the COVID‐19 pandemic. Studies 2A and 2B demonstrate that high vulnerability intensifies the anecdotal bias in different decision contexts. Study 3 replicates these findings and identifies negative emotional arousal as a key mechanism underlying this effect. Study 4 examines the moderating role of personal relevance, showing that when individuals make decisions for others (vs. themselves), high vulnerability does not lead to the anecdotal bias. Moreover, it is cognitive disruption and intuitive thinking caused by negative emotional arousal that increases reliance on anecdotal (vs. statistical) information. Finally, Study 5 demonstrates the moderating effect of mindfulness meditation, highlighting its role as a preemptive safeguard against this biased behavior. Theoretical contributions and practical implications of these findings are discussed.
F‐actin in the cuticular plate and junctions of auditory hair cells is regulated by ADF and cofilin to allow for normal stereocilia bundle patterning and maintenance
Authors: McGrath Jamis , Hawbaker Katelin , Perrin Benjamin J. 
Published: September 2024

AbstractAuditory hair cells, which convert sound‐induced vibrations in the inner ear into neural signals, depend on multiple actin populations for normal function. Stereocilia are mechanosensory protrusions formed around a core of linear, crosslinked F‐actin. They are anchored in the cuticular plate, which predominantly consists of randomly oriented actin filaments. A third actin population is found near hair cell junctions, consisting of both parallel and branched filaments. Actin depolymerizing factor (ADF) and cofilin‐1 (CFL1) proteins disassemble actin filaments and are required to regulate F‐actin in stereocilia, but their effect on cuticular plate and junctional actin populations is unclear. Here, we show that loss of ADF and CFL1 disrupts the patterning of stereocilia into orderly bundles and that this phenotype correlates with defective development of the cuticular plate and junctional actin populations. ADF/CFL1 continue to regulate these actin populations in mature cells, which is necessary for long‐term maintenance of hair cell morphology.
Nonsentinel lymph node metastases in cases of micrometastasis detected by sentinel lymph node biopsy after neoadjuvant chemotherapy
Authors: Shin Dong Seung , Ryu Jai Min , Lee Se Kyung , Yu Jonghan , Lee Jeong Eon , Kim Seok Won , Nam Seok Jin , Chae Byung Joo 
Published: September 2024

AbstractBackgroundThere is a clinical need to omit axillary lymph node dissection (ALND) when residual disease in sentinel lymph nodes (SLNs) is low after neoadjuvant chemotherapy (NAC). This study aimed to clarify the relationship between micrometastasis in SLNs after NAC and additional non‐SLN metastases by analyzing SLN biopsy results followed by ALND.MethodsThis retrospective study reviewed clinical records of patients who underwent breast cancer surgery between January 2010 and June 2022 after NAC at Samsung Medical Center. Of 3944 patients, 806 underwent SLN biopsy followed by ALND. Intraoperative frozen SLN biopsy results were examined, including the number and size of metastases in SLNs, and further investigated the number of additional non‐SLN metastases.ResultsAmong the 806 patients, 95 (11.8%) had micrometastasis on SLNs in frozen sections, of which 89 (93.7%) had clinically node‐positive (cN1‐3) breast cancer before NAC. Twenty‐three patients (24.2%) exhibited positive additional non‐SLNs after ALND. The presence of lymphovascular invasion (vs. absence; odds ratio [OR] = 4.02, p = .0151) and having two or more SLNs with micrometastasis (vs. a positive SLN; OR = 3.65, p = .0301) were significantly associated with additional non‐SLN metastases. Tumor subtypes and breast pathological complete response after NAC showed no correlation with the additional non‐SLN metastases.ConclusionThe study identified a 24.2% possibility of additional non‐SLN metastasis if micrometastases was detected in the SLN after NAC. This rate is significant, indicating that ALND cannot be omitted if low volume residual disease, such as micrometastasis, is identified in the SLN after NAC.
Aromaticity and Antiaromaticity Reversals between the Electronic Ground State and the Two Lowest Triplet States of Thiophene
Authors: Cummings Edward , Karadakov Peter B. 
Published: September 2024

AbstractIt is shown, by examining the variations in off‐nucleus isotropic magnetic shielding around a molecule, that thiophene which is aromatic in its electronic ground state (S0) becomes antiaromatic in its lowest triplet state (T1) and then reverts to being aromatic in T2. Geometry relaxation has an opposite effect on the aromaticities of the ππ* vertical T1 and T2: The antiaromaticity of T1 is reduced whereas the aromaticity of T2 is enhanced. The shielding picture around T2 is found to closely resemble those around certain second singlet ππ* excited states (S2), for example, those of benzene and cyclooctatetraene, thought to be “strongly aromatic” because of their very negative nucleus‐independent chemical shift (NICS) values. It is argued that while NICS values correctly follow the changes in aromaticity along the potential energy surface of a single electronic state, the use of NICS values for the purpose of quantitative comparisons between the aromaticities of different electronic states cannot be justified theoretically and should be avoided. “Strongly aromatic” S2 and T2 states should be referred to simply as “aromatic” because detailed comparisons between the properties of these states and those of the corresponding S0 states do not suggest higher levels of aromaticity.
4,4′‐Sulfonyldianiline Derived Aggregation‐Induced Emission Luminogen for the Detection of Ofloxacin
Authors: Patel Dhvani A. , Anand Thangaraj , Jali Bigyan R. , Sahoo Suban K. 
Published: September 2024

AbstractThe excessive use of antibiotic ofloxacin (Oflx) can cause serious detrimental effects to human health. Therefore, the utmost research priority is required to develop facile methods to detect Oflx. Herein, a V‐shaped aggregation‐induced emission (AIE) active Schiff base SDANA was introduced for the fluorescent turn‐on detection of Oflx. The Schiff base SDANA was synthesized by condensing 4,4′‐sulfonyldianiline with two equivalents of 2‐hydroxy‐1‐naphthaldehyde. The nearly non‐fluorescent SDANA in DMSO showed strong orange emission with the increase in HEPES buffer (H2O, 10 mM, pH 7.4) fractions in DMSO from 70 %–95 % due to the combined effects of AIE and ESIPT. The DLS and SEM analyses were performed to complement the formation of self‐aggregates of SDANA. With the addition of Oflx, the fluorescence emission of AIE luminogen (AIEgen) SDANA (λem=575 nm, λex=400 nm) was blue‐shifted and enhanced at 530 nm. The interactions of Oflx over the surface of SDANA aggregates disrupted the intramolecular charge transfer and aggregation morphology of SDANA, which gave a distinct fluorescence response to detect Oflx. The detection limit for Oflx was estimated as 0.81 μM, and the developed probe AIEgen SDANA was applied for the quantification of Oflx in human blood serum.
Room‐Temperature Columnar Tetragonal Self‐Assemblies based on Benzenetricarboxamide and Di‐ortho Substituted Azobenzene
Authors: Krishna KM Abhinand , Gupta Monika 
Published: September 2024

AbstractHere we report the design, synthesis, and photoresponsive behavior of supramolecular liquid crystalline (LC) materials based on benzenetricarboxamide and di‐ortho substituted azobenzene. Differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray scattering studies confirm the formation of columnar tetragonal mesophase at room‐temperature. Photoisomerization studies reveal the visible light responsiveness of compounds in solution. Furthermore, we demonstrate supramolecular gel formation, which undergoes irreversible gel‐sol transformation upon blue light irradiation, highlighting its potential for light‐triggered applications in the field of drug delivery, energy storage etc.
Visible‐Light Induced Selective C−H Arylation of 2‐Imino‐2H‐Chromene‐3‐Carbonitriles and Decarboxylative Ipso‐Arylation of 2‐Oxo‐2H‐Chromene‐3‐Carboxylic Acids
Authors: Sahoo Tanmoy , Banik Swarnayu , Vijaya Prasanna Dasari , Sridhar B. , Subba Reddy B. V. 
Published: September 2024

AbstractVisible‐light induced selective arylation of 2‐imino‐2H‐chromene‐3‐carbonitriles and decarboxylative ipso‐arylation of coumarin‐3‐carboxylic acids have been accomplished under mild conditions in the absence of either base or acid and oxidant. By employing blue LEDs as an excitation source, the aryl radicals are generated by Ru(II) complex through a single‐electron transfer process, which subsequently react with 2‐imino‐2H‐chromene‐3‐carbonitriles and 2‐oxo‐2H‐chromene‐3‐carboxylic acids to produce the desired products. This is the first report on selective arylation of conjugated systems without using either an acid or a base.
Lignin Nanofiber Flexible Carbon Aerogels for Self‐Standing Supercapacitors
Authors: Cho MiJung , Yiu Justine , Lin Li‐Ting , Hua Qi , Karaaslan Muzaffer A. , Renneckar Scott 
Published: September 2024

AbstractRenewable feedstocks are sought for clean technology applications, including energy storage applications. In this study, LignoForce™ lignin, a biobased aromatic polymer commercially isolated from wood, was fractioned into two parts using acetone, and the resulting lignin fractions had distinct thermo‐rheological behavior. These two fractionated lignins were combined in various ratios and transformed into nanofibers by electrospinning. Subsequently, electrospun fiber materials were disrupted by agitating the mats in water, and the materials were transformed into ultralight 3D aerogels through lyophilization and post‐process controlled heating. Using only this combination of two fractions, the morphology of lignin nanofibers was tailored by heat treatment, resulting in lignin aerogels with high flexibility and significant shape recovery properties. Various microscale structures of lignin fibers impacted the resulting physical properties of the elastic aerogel materials, such as resilience, compressive strength, and electrical conductivity for the corresponding carbonized samples. By exploiting lignin's sensitivity to heat and tailoring the thermal properties of the lignin through fractionation, the work provided an interesting path to form robust lignin‐derived functional materials without any toxic chemical additives and significant ability to serve as free‐standing electrodes with specific capacitance values better than some graphene‐based supercapacitors.
Activated Carbon Fiber Felt Composites for the Direct Air Capture of Carbon Dioxide
Authors: Korah Mani Modayil , Culp Kyle , Lackner Klaus S. , Green Matthew D. 
Published: September 2024

AbstractNegative emissions technologies to mitigate climate change require innovative solutions for the direct air capture (DAC) of CO2 from the atmosphere. K2CO3 readily reacts with CO2 to form KHCO3; however, bulk K2CO3 suffers from very slow sorption kinetics. By incorporating K2CO3 into activated carbon (AC) fiber felts, the sorption kinetics were significantly improved by increasing the surface area of K2CO3 in contact with air. The AC‐K2CO3 fiber composite felts are flexible, cheap, easy to manufacture, chemically stable, and show excellent DAC capacity and (de)sorption rates, with stable performance up to ten cycles. Cyclic testing was demonstrated with 4 h sorption and 0.5 h desorption intervals. The best composite felts collected an average of 478 μmol of CO2 per gram of composite during 4 h of exposure to ambient air (19 % relative humidity) that had a CO2 concentration of 400–450 ppm after regeneration at 125 °C in an air furnace. An increase in the dew point temperature from 0 to 12 °C decreased sorption performance of the composite felts by 40 %.
Understanding the Roles and Regulation Methods of Key Adsorption Species on Ni‐Based Catalysts for Efficient Hydrogen Oxidation Reactions in Alkaline Media
Authors: Li Jinchi , Yu Shuqi , Qing Chen , Wang Yao , Chen Yungui 
Published: September 2024

AbstractThis review focuses on recent advancements in the development and understanding of nickel‐based catalysts for the hydrogen oxidation reaction in alkaline media. Given the economic and environmental limitations associated with platinum group metals, nickel‐based catalysts have emerged as promising alternatives due to their abundance, lower cost, and comparable catalytic properties. The review begins with an exploration of the fundamental HOR mechanisms, emphasizing the key roles of the reactive species in optimizing the catalytic activity of Ni‐based catalysts. Thermodynamic and stability optimizations of nickel‐based catalysts are thoroughly examined, focusing on alloying strategies, heteroatom incorporation, and the use of various support materials to enhance their catalytic performance and durability. The review also addresses the challenge of catalyst poisoning, particularly by carbon monoxide, and evaluates the effectiveness of different approaches to improve poison resistance. Finally, the review concludes by summarizing the key findings and proposing future research directions to further enhance the efficiency and stability of nickel‐based catalysts for practical applications in anion exchange membrane fuel cells. The insights gained from this comprehensive analysis aim to contribute to the development of cost‐effective and sustainable catalysts and facilitate the broader adoption of AEMFCs in the quest for clean energy solutions.
Review of Ni‐Based Materials for Industrial Alkaline Hydrogen Production
Authors: Chen Cong , Olu Pierre‐Yves , Fan Ronglei , Shen Mingrong 
Published: September 2024

AbstractHydrogen has been recognized as a green energy carrier, which can relieve energy shortage and environmental pollution. Currently, alkaline water electrolysis (AWE) driven by renewable energy to produce large‐scale green hydrogen is a mainstream technology. However, tardy cathodic hydrogen evolution reaction (HER) and stability issue of catalysts make it challenging to meet the industrial requirements. Ni‐based materials have attracted wide attention, thanks to their low cost and rich tuning possibilities, and many efforts have focused on their activity and stability. However, due to the significant discrepancy between laboratory and industrial conditions, these catalysts have not been widely deployed in industrial AWE. In this review, we first introduce the differences between laboratory and industrial stage, especially concerning equipment, protocols and evaluation metrics. To shorten these gaps, some strategies are proposed to improve the activity and stability of the Ni‐based catalysts. Besides, some key issues related to the catalysts in industrial AWE device are also emphasized, including reverse‐current and foreign ions in the electrolyte. Finally, the challenges and outlooks on the industrial alkaline AWE are discussed.
Co@NC Chainmail Nanowires for Thermo‐ and Electrocatalytic Oxidation of 2,5‐Bis(hydroxymethyl)furan to 2,5‐Furandicarboxylic Acid
Authors: Zhu Bin , Wang Qiuge , Wang Jinggang , Yu Xiao , Zhang Jian , Chen Chunlin 
Published: September 2024

Abstract2,5‐Furandicarboxylic acid (FDCA) has emerged as an important bio‐based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5‐furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5‐hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5‐bis(hydroxymethyl)furan (BHMF), a non‐aldehyde and more stable precursor. This study pioneeringly reports nitrogen‐doped‐carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9 % conversion of BHMF with a 93.3 % yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9 % FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in‐situ generation of high‐valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon‐encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.
Chemoselective Intramolecular Rauhut‐Currier Reaction on a Labile Framework of Enone and Acrylamide: Tricyclohexylphosphine as a Stable and Economical Catalyst
Authors: Verma Rakesh Kumar , Bairwa Mansingh , Bharadwaj Kishor Chandra 
Published: September 2024

AbstractIntramolecular Rauhut‐Currier (IRC) reaction is an atom‐economical way of making carbocyclic and heterocyclic rings. However, its sensitivity towards electronic and steric parameters limits the reaction and stems the need for further development. Acrylamides have been one such left out of their sensitivity. Herein we report an IRC reaction, using acrylamide as a source of initial enolate. The cyclization has been achieved on a labile and challenging framework, prone to decomposition. Different control experiments have addressed the instability of the precursor. Protocol was further extendable to annulation for benzo analogs. We also report tricyclohexylphosphine (PCy3) as a stable, commercial, and easy‐to‐use nucleophilic catalyst in the field of IRC reactions as compared to earlier well‐established trimethyl and tributyl phosphines. Me3P and Bu3P although useful, are sensitive, prone to oxidation, and need careful handling. The protocol leads to the synthesis of piperidone and dihydroquinolone frameworks. A quick study to test the feasibility of catalyzing the Morita‐Baylis‐Hillman (MBH) reaction by PCy3 was also done successfully, although in moderate yields.
The application of match‐event and instrumented mouthguard data to inform match limits: An example using rugby union Premiership and rugby league Super League data from England
Authors: Sawczuk Thomas , Cross Matt , Owen Cameron , Roe Gregory , Stokes Keith , Kemp Simon , Tooby James , Allan David , Falvey Éanna , Starling Lindsay , Tierney Gregory , Tucker Ross , Jones Ben 
Published: September 2024

AbstractThe study aimed to illustrate how contact (from match‐event data) and head acceleration event (HAE) (from instrumented mouthguard [iMG]) data can be combined to inform match limits within rugby. Match‐event data from one rugby union and rugby league season, including all competitive matches involving players from the English Premiership and Super League, were used. Playing exposure was summarised as full game equivalents (FGE; total minutes played/80). Expected contact and HAE exposures at arbitrary thresholds were estimated using match‐event and iMG data. Generalised linear models were used to identify differences in contact and HAE exposure per FGE. For 30 FGEs, forwards had greater contact than backs in rugby union (n = 1272 vs. 618) and league (n = 1569 vs. 706). As HAE magnitude increased, the differences between positional groups decreased (e.g., rugby union; n = 34 and 22 HAE >40 g for forwards and backs playing 30 FGEs). Currently, only a relatively small proportion of rugby union (2.5%) and league (7.3%) players exceeded 25 FGEs. Estimating contact and HAEs per FGE allows policymakers to prospectively plan and model estimated overall and position‐specific loads over a season and longer term. Reducing FGE limits by a small amount would currently only affect contact and HAE exposure for a small proportion of players who complete the most minutes. This may be beneficial for this cohort but is not an effective HAE and contact exposure reduction strategy at a population level, which requires individual player management. Given the positional differences, FGE limits should exist to manage appropriate HAE and contact exposure.
Sleep‐related hypermotor seizures originating from the occipital lobe
Authors: Wadi Lara , Khweileh Mays , Agashe Shruti , Southwell Derek , Parikh Prachi , Frauscher Birgit 
Published: September 2024

AbstractWe present two unique cases of sleep‐related hypermotor epilepsy (SHE) originating from the occipital lobe. Patients with sleep‐related seizures and drug‐resistant occipital lobe epilepsy were identified from the ANPHY lab stereo‐electroencephalography (SEEG) research database at the Duke Comprehensive Epilepsy Center. We identified two young females with frequent sleep‐related focal seizures and occasional focal to bilateral tonic clonic seizures characterized by hypermotor movements. During wakefulness, the semiology also involved an elementary visual aura. They meet the 2016 diagnostic criteria for SHE, and SEEG monitoring with cortical stimulation mapping identified an epileptogenic zone (EZ) within the occipital lobe, with most seizures occurring out of NREM 2 sleep. Responsive neurostimulation devices were implanted, which indicated a trend for event detections in nocturnal periods. Extrafrontal SHE has characteristically been described in the temporal, insular‐opercular, and parietal lobes. Here, we demonstrate using SEEG‐confirmed EZ identification, that SHE can also originate in the occipital lobe. In patients with sleep‐related seizures and hypermotor behavior, occipital lobe seizures thus should not be excluded from the differential diagnosis. Key in identifying this rare localization is non‐frontal aura semiology and delay to motor symptoms, which may be supported by a visual field deficit and structural MRI abnormality.