bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Alzheimer's Association Global Biomarker Standardization Consortium (GBSC) plasma phospho‐tau Round Robin study
Authors: Ashton Nicholas J. , Keshavan Ashvini , Brum Wagner S. , Andreasson Ulf , Arslan Burak , Droescher Mathias , Barghorn Stefan , Vanbrabant Jeroen , Lambrechts Charlotte , Van Loo Maxime , Stoops Erik , Iyengar Shweta , Ji HaYeun , Xu Xiaomei , Forrest‐Hay Alex , Zhang Bingqing , Luo Yuling , Jeromin Andreas , Vandijck Manu , Bastard Nathalie Le , Kolb Hartmuth , Triana‐Baltzer Gallen , Bali Divya , Janelidze Shorena , Yang Shieh‐Yueh , Demos Catherine , Romero Daniel , Sigal George , Wohlstadter Jacob , Malyavantham Kishore , Khare Meenakshi , Jethwa Alexander , Stoeckl Laura , Gobom Johan , Kac Przemysław R. , Gonzalez‐Ortiz Fernando , Montoliu‐Gaya Laia , Hansson Oskar , Rissman Robert A. , Carrillo Maria C. , Shaw Leslie M. , Blennow Kaj , Schott Jonathan M. , Zetterberg Henrik 
Published: February 2025

AbstractINTRODUCTIONThe Alzheimer's Association Global Biomarker Standardization Consortium conducted a blinded case–control study to learn which phosphorylated tau (p‐tau) assays provide the largest fold‐changes in Alzheimer's disease (AD) versus non‐AD and show commutability in measuring patient samples and candidate certified reference materials (CRMs).METHODSThirty‐three different p‐tau assays measured paired plasma and cerebrospinal fluid (CSF) from 40 participants (25 with “AD pathology” and 15 with “non‐AD pathology” by CSF amyloid beta [Aβ]42/Aβ40 and p‐tau181 criteria). Four CRMs were assessed.RESULTSPlasma p‐tau217 demonstrated higher fold‐changes between AD and non‐AD than other p‐tau epitopes. Fujirebio LUMIPULSE G, UGOT IPMS, and Lilly MSD p‐tau217 provided the highest fold‐changes. Plasma p‐tau217 showed the strongest correlations between plasma assays (rho = 0.81–0.97). The CRMs were not commutable across assays.DISCUSSIONPlasma p‐tau217 showed larger fold‐changes and better accuracy for detecting AD pathology in symptomatic individuals, with greater cross‐platform agreement than other p‐tau variants. Further work is needed to develop suitable CRMs facilitating cross‐assay standardization.Highlights
Paired plasma and cerebrospinal fluid (CSF) samples from twenty‐five Alzheimer's disease (AD) and 15 non‐AD patients were measured blind.
Thirty‐three plasma assays were compared, for phosphorylated tau‐181 (p‐tau181), 205, 212, 217 and 231.
Plasma p‐tau217 consistently had the highest fold‐change and was best correlated between assays.
Plasma‐CSF correlations were weak to moderate.
There was lack of commutability for four candidate reference materials.
Pd‐Catalyzed Skeletal Rearrangement via C(sp3)−C(sp3) Activation to Access α,β‐Unsaturated δ/γ‐Lactone
Authors: Manna Kartic , Maji Suman , Sharma Akhilesh , Kumar Nikunj , Gupta Puneet , Maiti Debabrata 
Published: February 2025

AbstractThe activation of non‐polar aliphatic C−C bonds represents a significant challenge that remains to be addressed in the field of Pd(II) catalysis. In this study, we present a dual ligand approach as a means of addressing this issue. The process entails lactonization of cyclobutane and cyclopropane carboxylic acid via the activation of non‐polar C(sp3)−C(sp3) bond despite the high feasibility of both οrtho‐C(sp2)−H and β or γ ‐C(sp3)−H activation. Density Functional Theory (DFT) calculations were performed to reveal the mechanistic insights and elucidate the role of dual ligands in facilitating this challenging transformation.
Transient Dangling Active Sites of Fe(III)−N−C Single‐Atom Catalyst for Efficient Electrochemical CO2 Reduction Reaction
Authors: Qiu Yun‐Ze , Liu Xiao‐Meng , Li Wenying , Li Jun , Xiao Hai 
Published: February 2025

AbstractThe Fe single‐atom catalyst (SAC) with an oxidation state of III anchored on the N‐doped carbon substrate (Fe(III)−N−C) delivers superior activity for catalyzing the electrochemical CO2 reduction reaction (eCO2RR) to produce CO, but its mechanism remains contentious and the commonly adopted FeN4‐C model is not a conformant model for Fe(III)−N−C but for Fe(II)−N−C. Herein, employing the grand‐canonical ensemble modeling with the density functional theory method benchmarked against the high‐level wavefunction theory method, we first identify the conformant model for Fe(III)−N−C to be FeN1C3‐C, and we then unveil that the Fe(III)N1C3‐C SAC generates a novel type of dangling active site transiently under working conditions, in which the Fe single‐atom leaves from the anchoring site by breaking all the Fe−C bonds but retains a stable binding to the substrate by the Fe−N bond. Thus, we further elucidate that this flexible dangling active site of Fe(III)−N−C renders a convoluted reaction network with facile CO2 activation, which delivers superior activity for eCO2RR. Our findings provide a novel understanding of the structure–activity relationship for Fe−N−C and concrete insights into the design of highly active SACs.
Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh‐rate Zn Metal Anode
Authors: Xue Pan , Guo Can , Gong Wenbin , Chen Yuting , Chen Xiang , Li Xiaoge , Yang Jingyi , Zhang Qichong , Davey Kenneth , Zhu Kaiping , Mao Jianfeng , Guo Zaiping 
Published: February 2025

AbstractPolymer interphase on Zn anodes obviates dendrite growth and significant side reactions including corrosion and hydrogen evolution in aqueous zinc ion batteries (AZIBs), however has drawbacks of slow kinetics and large overpotential for Zn plating/stripping that prevent practical application especially under high‐rate conditions. Here, a multifunctional polymer interphase with fast kineticsis reported, using poly(phenazine‐alt‐pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π‐conjugated structure and enriched polar pyridine (conjugated cyclic −C=N−) and carbonyl (C=O) groups, preferentially adsorbs on the Zn anode to form a stable solid‐electrolyte interphase (SEI) layer in situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π‐conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de‐solvation and diffusion of Zn2+. As a result, the Zn metal anode with PPPA/ZnSO4 electrolyte exhibits high Coulombic efficiency of 98.3 % at current density of 20 mA  cm−2, and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm−2 and plating/stripping capacity of 5 mAh cm−2. The Zn||MnO2 full battery exhibited a discharge capacity of 74.4 mAh g−1 after 5000 cycles at the current density of 2000 mA g−1, demonstrating practical feasibility. It is concluded that judicious engineering of polymer additives and interphase will benefit the development of commercial AZIBs with fast kinetics for high‐rate applications.
Divergent Total Syntheses of Six Crinipellin‐Type Diterpenoids through Tandem 4π‐Electrocyclization/Dicycloexpansion
Authors: Ke Tian , Hou Si‐Hua , Wang Yun‐Peng , Fang Kun , Hu Jing‐Han , Lu Ka , Tu Yong‐Qiang 
Published: February 2025

AbstractCrinipellins are a significant class of naturally occurring highly congested tetraquinane diterpenoids, with many members exhibiting bio‐important antibacterial and anticancer activities. However, their complex structures, particularly their dense 5/5/5/5 tetracyclic frameworks, have made efficient synthesis challenging, leading chemists to attempt to create highly efficient and divergent routes. This study presents a concise, divergent synthesis of six crinipellins, completed in just 9–11 steps using commercially available materials. Particular highlights include: (1) a vital one‐step 4π‐electrocyclization/dicycloexpansion cascade that rapidly constructs the angular/fused tetraquinane scaffold with two contiguous quaternary carbons, and (2) strategic functionalizations through iso‐propylation, methylation, and Wacker oxidation/dehydrogenation, enabling the divergent syntheses of the six crinipellin members without using protecting groups. This approach provides a versatile platform for accessing additional crinipellin derivatives, which we believe will benefit medicinal and biological research.
The Last Piece of the Puzzle: Access to 7‐Connected Zirconium Metal–Organic Frameworks for Hexane Separation
Authors: Tang Xianhui , Jia Lei , Wang Xiaoliang , Su Shengyi , Chen Yongwei , Kong Xiang‐Jing , Ye Zi‐Ming , Xie Haomiao , Gong Wei , Du Enping , Liu Yan , Kirlikovali Kent O. , Farha Omar K. , Cui Yong 
Published: February 2025

AbstractZirconium metal–organic frameworks (Zr‐MOFs) exhibit a wide range of Zr6 cluster connectivities, from 3‐connected to 12‐connected, enabling diverse structural designs. However, odd‐numbered connectivities, especially the 7‐connected Zr‐MOFs, are exceptionally rare due to geometric symmetry challenges. To address this, we developed a geometric pre‐assembly strategy to achieve targeted cluster connectivity. Using this approach, we synthesized NU‐5001 {[Zr6O4(OH)4(H4‐L)2]}, a Zr‐MOF featuring 7‐connected Zr6 clusters, derived from the precursor 6‐connected Zr‐MOF, NU‐5000 {[Zr6O4(OH)4(H3‐L)2]}. NU‐5000, constructed with a tritopic chiral linker H3‐L {(R)‐4,4’,4’’‐[6’‐chloro‐2,2’‐diethoxy‐(1,1’‐binaphthalene)‐4,4’,6‐triyl]tribenzoic acid}, forms a (3,6)‐connected ant topology. Introducing a tetratopic chiral linker, 1,1’‐bi‐2‐naphthol tetracarboxylic acid H4‐L {(R)‐4,4’,4’’,4’’’‐[2,2’‐diethoxy‐(1,1’‐binaphthalene)‐4,4’,6,6’‐tetrayl]tetrabenzoic acid}, enabled an additional connection, resulting in NU‐5001 with a (3,4,7)‐connected topology. The H4‐L linker acts as either fully 4‐connected or 3‐connected with one arm uncoordinated. Additionally, NU‐5001M {[Zr6O4(OH)4(H4‐L) (H3‐L)]}, an isostructural variant, was synthesized using a mix of H3‐L and H4‐L linkers. NU‐5001’s unique pore structure and slight flexibility enable distinct adsorption behaviors for hexane isomers, highlighting its potential for kinetic separations. This work completes the Zr6 cluster connectivity landscape and demonstrates the feasibility of tuning Zr‐MOF connectivities through rational linker design, paving the way for rare, low‐symmetry frameworks with tailored properties.
H‐Bonds in Carbon Quantum Dot‐anchored C3N5 to Boost Proton‐Coupled Electron Transfer for Piezoelectric‐Driven Hydrogen Peroxide Synthesis under Ambient Conditions
Authors: Li Zhi , Tong Kangbo , Dong Haojie , Li Yatai , Wang Kai , Ding Tengda , Yun Yang , Zhou Yingtang , Zhu Mingshan 
Published: February 2025

AbstractTuning proton‐coupled electron transfer (PCET) is a promising strategy to boost the oxygen reduction reaction (ORR) for hydrogen peroxide (H2O2) synthesis, but the slow transmission rate of protons and electrons to active sites remains a significant bottleneck. To address this, we developed an H‐bond‐driven PCET process based on carbon quantum dot‐anchored C3N5 (CQDs‐C3N5) for piezo‐catalytic H2O2 synthesis. CQDs‐C3N5 exhibited a remarkable piezo‐catalytic synthesis rate of 5025 μmol g−1 h−1 under ambient conditions, surpassing that of most reported piezoelectric materials. This efficiency is attributed to the intermolecular H‐bonds between CQDs and C3N5, which significantly accelerate PCET in the ORR. The piezoelectric‐generated charges, from the dipole field of the C3N5 plane, and protons in water, were rapidly transferred to the C rings of CQDs via H‐bond networks. This process facilitated the adsorption of oxygen onto the C2 sites adjacent to the carboxyl groups of CQDs, which in turn led to the formation of H2O2 through a rapidly protonated, indirect 2e− pathway. Additionally, a piezo‐self‐Fenton reaction system was constructed for oxytetracycline‐rich wastewater purification, with effectively effects on chemical oxygen demand, antibiotic‐resistant bacteria and antibiotic‐resistant genes degradation, etc. This study highlights the critical role of H‐bond networks for tuning PCET in the ORR and provides a comprehensive understanding for the precise control of catalytic reaction kinetics through molecular structural engineering.
Flexible and Recyclable Epoxy Vitrimer With Improved Thermal Conductivity for Thermal Management
Authors: Wang Dong liang , Zhan Lebin , Zheng Zhihong , Zhang Jingyun , Yang Songwei , Luo Fubin , Hu Ting 
Published: February 2025

ABSTRACTThe accelerated evolution of electronic devices has resulted in an increased demand for thermal management materials. In this study, methoxy polyethylene glycol (MPEG) was introduced into a covalent adaptable epoxy network. It is demonstrated that the epoxy material becomes softer as the amount of MPEG content is increased, specifically exhibiting excellent flexibility with an impressive elongation at break of 444.68%. The thermal conductivity of the epoxy resin was enhanced by the incorporation of boron nitride (BN) filler, and the findings demonstrated that the thermal conductivity of the composites was markedly elevated to 3.34 Wm−1 K−1 when the proportion of BN filler reached 50%. The potential use of such composites as thermal management materials is demonstrated in their application for heat dissipation in LED chips. In addition, the covalent adaptive network enables the decomposition of the composites prepared in this study under chemical conditions, with the fillers subsequently being separated by physical filtration. This approach offers a potential pathway toward the sustainable development of thermal management materials.
Electrochemical Hydrogen Evolution with Metal–Organic Framework‐Derived Catalysts: Strategies for d‐Band Modulation by Electronic Structure Modification
Authors: Singh Baghendra , Ansari Toufik , Indra Arindam 
Published: February 2025

AbstractThe effective use of metal‐organic framework (MOF)‐based materials in the electrocatalytic hydrogen evolution reaction (HER) relies on the understanding of their structural and electronic properties. While the structure and morphology of MOF‐derived catalysts significantly impact HER activity, tuning the d‐band structure through electronic structure modulation has emerged as a key factor in optimizing catalytic performance. Techniques such as composition tuning, heteroatom doping, surface modification, and interface engineering were found to be effective methods for manipulating the electronic configuration and, in turn, modulating the d‐band. This review systematically explores the design strategies for MOF‐derived catalysts by focusing on electronic structure modulation. It provides a detailed discussion of the various methods – used to modulate the electronic structure. Furthermore, the review establishes the relationship between d‐band tuning, Gibbs free energy, and electronic structure modulation, supported by both spectroscopic and theoretical evidences.
Twists and Loops: Exploring Lemniscular Vinylogous Benzioctaphyrin(2.0.1.0.2.0.1.0)
Authors: Vishwakarma Rampal , Jana Narayan Ch. , Das Mainak , Srinivasan A. 
Published: February 2025

AbstractOctaphyrins, offer unparalleled opportunities for designing complex molecular architectures with distinct physical and chemical properties. However, lemniscate‐shaped benzioctaphyrins remain scantily explored, leaving a gap in understanding how this unconventional geometry/shape influences macrocyclic behaviour. In this study, we explore the design, synthesis, and structural properties of benzioctaphyrin by incorporating the bis‐E‐stilbene unit, where a vinylene π‐bridge connects phenylene rings. The benzioctaphyrin(2.0.1.0.2.0.1.0) adopts a lemniscate topology to alleviate steric strain, with protonation inducing conformational desymmetrization. The presence of a meta‐phenylene unit thwarts the global π‐conjugation, rendering the macrocycle nonaromatic. Notably, this work represents the first exploration of the oligomeric vinylene group in benzioctaphyrin framework. It offers new insights into how structural modifications influence topology, π‐electron delocalization, and macrocyclic flexibility, setting the stage for future advancements in topologically unique porphyrinoid systems.
Oxidation‐Condensation Tandem Catalysis via a Multifunctional Cu‐Based Metal‐Organic Framework
Authors: Kim Hyeonsu , Son Younghu , Hwang Dogyeong , Rao Purna Chandra , Kim Younghoon , Yoon Minyoung 
Published: February 2025

AbstractThe development of heterogeneous catalysts for tandem reactions remains a significant challenge for practical applications, primarily due to the need for multiple isolated catalytic sites. This study presents a novel metal‐organic framework (MOF), Cu‐AIPA, formulated as Cu(AIPA)(DMF)2 (AIPA: 2‐amino isophthalic acid, DMF: N, N‐dimethylformamide). The Cu‐AIPA framework integrates three distinct catalytic mechanisms: redox activity, Brønsted basicity, and Lewis acidity. The structure of Cu‐AIPA features redox‐active Cu(II) centers and Brønsted basic sites, enabling the sequential transformation of alcohols to aldehydes and their subsequent condensation into imines. The close spatial arrangement of these redox‐active/Lewis acidic and basic sites within the confined pores of Cu‐AIPA facilitates efficient tandem catalysis. This process involves oxidizing benzyl alcohol to benzaldehyde using TEMPO without requiring an external base, followed by amine condensation. Compared with HKUST‐1, another Cu‐based MOF with a high surface area, Cu‐AIPA demonstrated superior catalytic performance at room temperature. Recyclability tests revealed that Cu‐AIPA retained over 90 % conversion efficiency across at least three catalytic cycles. This study highlights the potential of MOFs incorporating multiple catalytic sites and confined pore structures for tandem reactions, emphasizing their potential for scalable and sustainable industrial applications.
A generalized extreme value approach for the analysis of stationary climatic covariate in a Mediterranean city
Authors: Cherif Semia 
Published: February 2025

AbstractExtreme value theory (EVT) is used as univariate extreme value analysis (EVA) in order to analyze and model the covariates temperature, relative humidity (RH) and the thermal comfort index (humidex) issued from a dataset of 38 years in Tunis. It is a South Mediterranean area known as a hotspot for climate change. The best approach is to reduce the data considerably by taking annual block maxima from mean monthly data. It will converge to a generalized extreme value distribution in order to estimate the return levels of the studied parameters. The stationarity of the series are checked by augmented Dickey‐Fuller test. The modeling of the three parameters shows a Weibull distribution pattern. The extreme/maximum monthly means temperature of 30.2°C and humidex of 39.4 have a common return level between 300 and 350 years. The highest mean monthly RH of 86.0% is expected to be exceeded every 50 years. For the next 38 years, the maxima monthly mean temperatures are expected to be stable, and the maxima monthly mean RH values, as well as the humidex monthly mean maxima are expected to decrease. The percentile air temperature hot day (TX90p) and night (TN90p) indices show globally linear upward trends and the ones of cold days (TX10p) and cold nights (TN10p) have a downward trend. The diurnal yearly temperature range shows an almost flat trend for its evolution through the years of study.
Suicidality in Autistic Adolescents and Adults: Sleep the Unexplored Connection?
Authors: Richdale Amanda L. , Morris Eric M. J. , Lawson Lauren P. 
Published: February 2025

ABSTRACTDespite substantial evidence linking insomnia with increased suicidality in non‐autistic populations, its role in autism remains under‐explored. Poor sleep, most commonly insomnia symptoms (hereafter insomnia), is a significant issue in autism, affecting up to 80% of autistic children and adults, compared with 30%–50% of children and about 45% of adults in the general population. Sleep, along with quality of life, anxiety, depression, and social well‐being, is a top mental health research priority for autistic adults. These factors are all significantly associated with insomnia in both autistic and non‐autistic individuals. Current findings highlight the association between depression, psychosocial factors, and suicidality in autistic individuals. Key factors in suicidality for autistic people include increased autistic traits, loneliness, lack of social support, and experiences such as camouflaging and burnout. What is under‐explored is the role of sleep in suicidality and mental health in autism. Effective psychological interventions for insomnia in autistic individuals are lacking, and there is limited understanding of whether treating insomnia can reduce suicidality. Only two pilot studies have investigated insomnia treatments for autistic adults. In this commentary, we argue that, given the high rate of suicidality in autism and the potential role of insomnia, it is crucial to investigate whether insomnia contributes to suicidality in autistic people and if addressing sleep through prevention strategies, supports, and interventions improves outcomes. Collaboration with the autistic community is essential for addressing this knowledge gap and developing effective interventions.
Multifunctional Surface Enhanced Raman Scattering Substrate Fe 3O4 @AgNPs@MIL‐101 for Pretreatment and Rapid Detection of Pesticide Residues on the Surface of Fruit Peels
Authors: Zhang Mingyu , Tian Yizhuo , Liu Sijia , Wang Yu , Li Haiyan , Chen Yafei , Gao Qing , Wang Xinli , Chen Mingli 
Published: February 2025

ABSTRACTA multifunctional surface‐enhanced Raman scattering substrate Fe3O4@AgNPs@MIL‐101 was prepared. Rapid SERS detection of pesticide residues was realized by direct pre‐enrichment and separation on the peel surface. MIL‐101 has an ortho‐octahedral framework and large pore size, which endowed Fe3O4@AgNPs@MIL‐101 with the ability to rapidly adsorb and separate positively charged targets. The introduction of tannic acid realized the in situ growth of AgNPs on the backbone, to modulate the electromagnetic enhancement. Pesticide molecules were adsorbed onto the surface of AgNPs mediated by central S atoms, accompanied by the interaction between pesticide molecules and AgNPs, the corresponding SERS signals of different pesticides were observed. Together with the introduction of magnetic coating Fe3O4, the molecules were enriched in the hotspot and separated to further enhance the SERS performance. Magnet instead of centrifugation was used to simultaneously perform surface extraction and sample separation for a noninvasive, rapid, immediate, and portable assay. The method was accomplished in measurement of thiram and thiabendazole on apple and tangerine epidermis, and the limits of detection (LODs) were 20 ng/cm2 and 4 μg/cm2, respectively. The recovery was reasonable, and it showed that the procedure is valuable for the rapid and nondestructive surface analysis of residual chemicals.