bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual Cocatalytic Sites Synergize NiFe Layered Double Hydroxide to Boost Oxygen Evolution Reaction in Anion Exchange Membrane Water Electrolyzer
Authors: Shi Yue , Song Lumin , Liu Yan , Wang Tiantian , Li Caixia , Lai Jianping , Wang Lei 
Published: October 2024

AbstractNickel‐iron layered double hydroxide (LDH) is a promising cost‐efficient catalyst to replace noble metals for alkaline oxygen evolution reaction (OER), yet its intrinsic activity under high current density conditions is not satisfactory, which greatly constrains the industrial application of NiFe LDH catalysts. Herein, a new class of integrated Co and W co‐doped NiFe LDH catalysts is reported with dual cocatalytic sites for alkaline OER catalysis. The optimized Co2.8, W3.8‐NiFe LDH integrated catalyst has superior alkaline OER activity (255 mV@1000 mA cm−2) and excellent catalytic stability (200 h@500 mA cm−2). The turnover frequency value of Co2.8, W3.8‐NiFe LDH can reach 4.02 s−1 at 1.49 V versus RHE, which is 9.6 times higher than that of NiFe LDH and superior to the noble metal catalysts. Moreover, it can achieve 1.0 A cm−2 at 1.86 V and maintain 300‐h stable operation in anion exchange membrane water electrolyzer. Theoretical and experimental studies indicate that W sites promote the *OH adsorption and Co sites favor protons desorption of OH*. These dual cocatalytic sites jointly promote *O coverage, effectively accelerating alkaline OER kinetic.
Homogeneous Complexation Strategy to Manage Bromine for High‐Capacity Zinc–Bromine Flow Battery
Authors: Xiong Qinghua , Huang Mingbao , Ren Tianlu , Wu Shixi , Wang Wenfeng , Xiang Zhipeng , Wan Kai , Fu Zhiyong , Liang Zhenxing 
Published: October 2024

AbstractZinc–bromine flow batteries (ZBFBs) have received widespread attention as a transformative energy storage technology with a high theoretical energy density (430 Wh kg−1). However, its efficiency and stability have been long threatened as the positive active species of polybromide anions (Br2n+1−) are subject to severe crossover across the membrane at a high concentration. Herein, a novel highly hydrophilic complexing agent, N‐methyl‐N, N‐bis(2‐hydroxyethyl)‐1‐propanaminium bromide (PMDA), is developed to effectively manage bromine in a homogeneous posolyte, which realizes a low bromine crossover at a high operating concentration in ZBFBs. Both theoretical and experimental results suggest that the PMDA interacts with Br2n+1− and forms a larger‐size complex PMDABr2n+1. When adding 0.40 m PMDA, the bromine stays homogeneous at a high concentration up to 1.20 m, and its permeability is remarkably decreased by 74%. For demonstration, the ZBFB achieves a operating capacity record of 57.2 Ah L−1 in a homogeneous bromine posolyte with a high Coulombic efficiency of ≈90.0% and superior cycling stability (capacity retention rate of 100.0% per cycle). This work provides one innovative bromine management strategy to realize a high capacity and superior stability in ZBFBs.
Comprehensive Understanding of Steric‐Hindrance Effect on the Trade‐Off Between Zinc Ions Transfer and Reduction Kinetics to Enable Highly Reversible and Stable Zn Anodes
Authors: Hu Nan , Tao Jin , Tan Yi , Song Huawei , Huang Dan , Liu Penggao , Chen Zhengjun , Yin Xucai , Zhu Jinliang , Xu Jing , He Huibing 
Published: October 2024

AbstractThe electrode interface concentration polarization attributed to the contradiction between sluggish mass transfer process and rapid electrochemical reduction kinetics significantly restricts the practical application of Zn anode. Creating a moderate Zn ions transfer and reduction chemistry is essential for durable zinc‐ion batteries. In this work, this trade‐off effect is realized by selecting large‐size 4‐Aminomethyl cyclohexanecarboxylic acid (AMCA) molecule as the electrolyte additive. Intriguingly, AMCA molecules reorganize the Zn2+ solvation structure via the robust coordination with Zn2+ and reconstruct H‐bond networks, giving a pulled desolvation process. Meanwhile, AMCA enlarges the Zn2+ solvation size with a push force, confining the rapid electrochemical reduction kinetics. The balanced chemical environment is maintained via the moderate pull‐push interplay. Besides, AMCA can anchor on zinc surface to create a water‐poor microenvironment, fostering homogeneous Zn (002) deposition and effectively restricting water‐induced side‐reactions. Notably, the Zn||Zn symmetric cell with AMCA operates stably over 167 days at 20 mA cm−2. Moreover, the Zn||VOX full cell employed AMCA ensures outstanding capacity retention of 99.15% after 590 cycles at 2 A g−1, even with low N/P (4.3), lean electrolyte (50 µL mAh−1) and ultrathin Zn foil of 10 µm. This work reveals unique insights into the balanced interfacial chemistry design toward high‐performance zinc batteries.
A combination of covalent and noncovalent restricted‐intramolecular‐rotation strategy for supramolecular AIE‐type photosensitizer toward photodynamic therapy
Authors: Li Qingfang , Zhang Peijuan , Wang Pingxia , Yan Chaochao , Wang Kaige , Yang Wanni , Dang Dongfeng , Cao Liping 
Published: October 2024

AbstractPhotodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation‐caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted‐intramolecular‐rotation strategies to develop supramolecular PSs with aggregation‐induced emission (AIE) characteristics. Firstly, a water‐soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single‐molecule‐level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single‐layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2−•) and singlet oxygen (1O2) upon white‐light irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2−• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type‐I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE‐type PS to exhibit strong photo‐induced cytotoxicity upon white‐light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.
Heritability in the Rhesus Macaque (Macaca mulatta) Vertebral Column
Authors: Villamil Catalina I. , Negrón Jeziel J. , Middleton Emily R. 
Published: October 2024

ABSTRACTThe vertebral column plays a central role in primate locomotion and positional behavior. Understanding its evolution, therefore, has the potential to clarify evolutionary processes that have occurred in the primate lineage as well as the specific behaviors of extinct primates. However, to understand primate vertebral anatomy, it is important to determine how much of this anatomy is heritable and how much develops as a response to environmental factors during life. We estimated heritability for vertebral counts as well as typical cervical, thoracic, and lumbar elements from 210 individuals from the pedigreed Cayo Santiago Macaca mulatta skeletal collection. We found moderate heritability of vertebral counts (h2 = 0.216–0.326), but with strong heritability of the type of variation (e.g., a tendency to meristic or homeotic change) in the vertebral count (h2 = 0.599), suggesting a possible explanation for high variability in vertebral numbers among the hominoids in particular. The moderate heritability of vertebral count also suggests that vertebral count is an unsuitable metric for estimating the ancestral state for some taxa. We found strong heritability in the morphology of cervical and upper lumbar zygapophyseal facets (h2 = 0.548–0.550) and the thoracic spinous processes (h2 = 0.609–0.761), including high heritability of the spinous process angle in the upper thoracic and upper lumbar elements (h2 = 0.649–0.752). We suggest these are related to maintaining stability in the cervical and lumbar regions, and reducing motion in the thoracic region, respectively. We propose that spinous processes may contain greater phylogenetic information, whereas transverse processes may contain greater information of function ‘in life’. We also found important size effects, suggesting that size is the most heritable component of overall form and largely responsible for intertrait differences. This suggests that it is inappropriate to indiscriminately remove size effects from morphological comparisons.
Dementia risk scores, apolipoprotein E, and risk of Alzheimer's disease: One size does not fit all
Authors: Andrews Shea J. , Boeriu Ana I. , Belloy Michael E. , Renton Alan E. , Fulton‐Howard Brian , Brenowitz Willa D. , Yaffe Kristine ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: October 2024

AbstractINTRODUCTIONEvaluating the generalizability of dementia risk scores, primarily developed in non‐Latinx White (NLW) participants, and interactions with genetic risk factors in diverse populations is crucial for addressing health disparities.METHODSWe analyzed the association of the Cardiovascular Risk Factors, Aging, and Incidence of Dementia (CAIDE) and modified CAIDE (mCAIDE) scores with dementia risk using logistic regression models stratified by race/ethnicity in National Alzheimer's Coordinating Center (NACC) and Alzheimer's Disease Neuroimaging Initiative (ADNI), and assessed their interaction with apolipoprotein E (APOE).RESULTSHigher CAIDE scores were associated with an increased risk of dementia in Asian, Latinx, and NLW participants but not in Black participants. In contrast, higher mCAIDE scores were also associated with an increased risk of dementia in Black participants. Unfavorable mCAIDE risk profiles exacerbated the apolipoprotein E*ε4 (APOE*ε4) risk effect and attenuated the APOE*ε2 protective effect.DISCUSSIONOur findings underscore the importance of evaluating the validity of dementia risk scores in diverse populations for their use in personalized medicine approaches to promote brain health.Highlights
Dementia risk scores demonstrate race/ethnic‐specific effects on dementia risk.
Unfavorable modifiable risk profiles moderate the effect of APOE on dementia risk.
Dementia risk scores need to be validated in diverse populations.
Arterial spin labeling perfusion MRI in the Alzheimer's Disease Neuroimaging Initiative: Past, present, and future
Authors: Thropp Pamela , Phillips Eliana , Jung Youngkyoo , Thomas David L. , Tosun Duygu ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: October 2024

AbstractOn the 20th anniversary of the Alzheimer's Disease Neuroimaging Initiative (ADNI), this paper provides a comprehensive overview of the role of arterial spin labeling (ASL) magnetic resonance imaging (MRI) in understanding perfusion changes in the aging brain and the relationship with Alzheimer's disease (AD) pathophysiology and its comorbid conditions. We summarize previously used acquisition protocols, available data, and the motivation for adopting a multi‐post‐labeling delay (PLD) acquisition scheme in the latest ADNI MRI protocol (ADNI 4). We also detail the process of setting up this scheme on different scanners, emphasizing the potential of ASL imaging in future AD research.Highlights
The Alzheimer's Disease Neuroimaging Initiative (ADNI) adopted multimodal arterial spin labeling magnetic resonance imaging (ASL MRI) to meet evolving biomarker requirements.
The ADNI provides one of the largest multisite, multi‐vendor ASL data collections.
The ADNI 4 incorporates multi‐post‐labeling delay ASL techniques to jointly quantify cerebral blood flow and arterial transit time.
ADNI 4 ASL MRI protocol is apt for detecting early Alzheimer's disease with cerebrovascular pathology.
A Proteomics Pipeline for Generating Clinical Grade Biomarker Candidates from Data‐Independent Acquisition Mass Spectrometry (DIA‐MS) Discovery
Authors: Fu Qin , Vegesna Manasa , Sundararaman Niveda , Damoc Eugen , Arrey Tabiwang N. , Pashkova Anna , Mengesha Emebet , Debbas Philip , Joung Sandy , Li Dalin , Cheng Susan , Braun Jonathan , McGovern Dermot P. B. , Murray Christopher I. , Xuan Yue , Van Eyk Jennifer E. 
Published: October 2024

AbstractClinical biomarker development has been stymied by inaccurate protein quantification from mass spectrometry (MS) discovery data and a prolonged validation process. To mitigate these issues, we created the Targeted Extraction Assessment of Quantification (TEAQ) software package that uses data‐independent acquisition analysis from a discovery cohort to select precursors, peptides, and proteins that adhere to analytical criteria required for established targeted assays. TEAQ was applied to DIA‐MS data from plasma samples acquired on a new high resolution accurate mass (HRAM) mass spectrometry platform where precursors were evaluated for linearity, specificity, repeatability, reproducibility, and intra‐protein correlation based on 8‐ or 11‐point loading curves at three throughputs. This data can be used as a general resource for developing other targeted assays. TEAQ analysis of data from a case and control cohort for inflammatory bowel disease (n=492) identified 1110 signature peptides for 326 quantifiable proteins from the 1179 identified proteins. Applying TEAQ analysis to discovery data will streamline targeted assay development and the transition to validation and clinical studies.
Synthesis and Structure Determination by 3D Electron Diffraction of the Extra‐large Pore Zeolite ITQ‐70
Authors: Tirado Juan I. , Sala Andrés , Bordes Antonio , Pratim Das Partha , Palatinus Lukáš , Nicolopoulos Stavros , Jordá Jose L. , Vidal‐Moya Alejandro , Blasco Teresa , Sastre German , Valencia Susana , Rey Fernando 
Published: October 2024

AbstractIn this study, we present the synthesis, characterization, and structural analysis of a novel zeolite, ITQ‐70, using 3D electron diffraction. This unique material was synthesized under alkaline conditions, employing tetrakis(diethylamino)phosphonium as an organic structure‐directing agent, leading to the formation of a pure silica zeolite. ITQ‐70 is distinguished by its extra‐large pore apertures, which extend along all three axes and intersect one to the other. A notable feature of this zeolite is the presence of structurally ordered defects in very high concentrations (38 % of the silicon atoms). As a result, ITQ‐70 exhibits the lowest framework density (10.0 T/1000 Å3) ever reported for any zeolite except RWY (7.6 T/1000 Å3), which contains sulfur instead of oxygen connecting T‐atoms.
De(sulfon)amidative Cyclization: The Synthesis of Dibenzolactams and Dibenzosultams for Organic Light Emitting Diode Materials
Authors: Luo Anping , Li Zhijie , Chen Haohua , Wang Ya , Liu Xiaoyu , Bin Zhengyang , Yang Yudong , You Jingsong 
Published: October 2024

AbstractThis study addresses a challenge in organic synthetic chemistry: the direct cleavage of amide bonds, which is typically hampered by the thermodynamic stability of the C(Ar)−C(acyl) bond. Previous methods often rely on “CO” extrusion‐jointing transition metal‐catalyzed process and require activated tertiary amides, limiting their applicability due to incompatibility with reactive functional groups such as halogens. Herein, we report a transition metal‐free approach for the deamidative cyclization of biaryl diamides via a radical process, yielding dibenzolactam derivatives. Along this line, we have developed the desulfonamidative cyclization of biaryl disulfonamides to produce dibenzosultams through direct nucleophilic aromatic substitution, demonstrating high selectivity for unsymmetrical structures. Additionally, unsymmetrical sulfamoyl biaryl amides, containing both amide and sulfonamide functionalities, can selectively undergo desulfonamidative coupling with the amide to form dibenzolactams, which offers a complementary synthetic pathway to unsymmetric dibenzolactams. These protocols exhibit excellent compatibility with reactive functional groups, including halogens, providing an innovative synthetic toolbox for the development of thermally activated delayed fluorescence (TADF) materials used in organic light emitting diodes (OLEDs). DMAC‐PDO, incorporating a dibenzolactam as the acceptor unit, serves as an efficient blue TADF emitter with a maximum external quantum efficiency (EQEmax) of 23.4 %.
Formamidinium Incorporates into Rb‐based Non‐Perovskite Phases in Solar Cell Formulations
Authors: Gunes Ummugulsum , Hope Michael A. , Zhang Yuxuan , Zheng Likai , Pfeifer Lukas , Grätzel Michael , Emsley Lyndon 
Published: October 2024

AbstractOrganic‐inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI3), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non‐perovskite phase complicates the application of FAPbI3 in solar cells. To remedy this, alkali metal cations, most often Cs+, Rb+ or K+, are included during perovskite synthesis to stabilize the photoactive phase. The atomic‐level mechanisms of stabilization are complex. While Cs+ dopes directly into the perovskite lattice, Rb+ does not, but instead forms an additional non‐perovskite phase, and the mechanism by which Rb confers increased stability remains unclear. Here, we use 1H−87Rb double resonance NMR experiments to show that FA+ incorporates into the Rb‐based non‐perovskite phases (FAyRb1‐yPb2Br5 and δ‐FAyRb1‐yPbI3) for both bromide and iodide perovskite formulations. This is demonstrated by changes in the 1H and 87Rb chemical shifts, 1H−87Rb heteronuclear correlation spectra, and 87Rb{1H} REDOR spectra. Simulation of the REDOR dephasing curves suggests up to ~60 % FA+ incorporation into the inorganic Rb‐based phase for the bromide system. In light of these results, we hypothesize that the substitution of FA+ into the non‐perovskite phase may contribute to the greater stability conferred by Rb salts in the synthesis of FA‐based perovskites.
Integrated Monomer Synthesis and Framework Assembly: Achieving Isoreticular Modulation of Hydrogen‐Bonded Organic Frameworks
Authors: Shang Yanxue , Ma Lishuang , Kang Zixi , Wu Yanfang , Fan Weidong , Wang Rongming , Yan Zifeng , Sun Daofeng , Zeng Jingbin 
Published: October 2024

AbstractSystematic construction of isoreticular hydrogen‐bonded organic frameworks (HOFs) promises tailored material properties crucial for diverse applications, yet is challenging due to the weak, flexible, and non‐directional nature of hydrogen bonds. Herein, we develop an “integrated monomer synthesis‐framework assembly” (ISA) methodology for constructing a series of isoreticular HOFs. Unlike traditional methods where monomers are first synthesized and then assembled into HOFs, the ISA system employs dicyandiamide rigid hydrogen‐bonded hexameric clusters as connecting nodes to covalently react with planarized C3‐symmetric cyano‐precursors (C3‐CPs) to generate diaminotriazine (DAT) monomers, while simultaneously inducing the directional assembly into isoreticular (6,3)‐net hcb topological DAT‐C6‐HOFs. The pore sizes and microenvironments of the resulting DAT‐C6‐HOFs can be precisely tuned by varying the structural modulation (length and steric hindrance) of the π‐bridge on C3‐CPs, enabling highly selective sensing towards perfluorooctanoic acid over other homologous molecules, that are difficult to be separated and detected by chromatography. Overall, the ISA methodology facilitates the scalable creation of families of isostructural HOFs and provides a customized structural platform for investigating factors beyond topology that impact the capturing, releasing, and responding to guest molecules.
Triflic Acid‐Catalyzed Dehydrative Amination of 2‐Arylethanols with Weak N‐Nucleophiles in Hexafluoroisopropanol
Authors: Van Hoof Max , Mayer Robert J. , Moran Joseph , Lebœuf David 
Published: October 2024

AbstractThe catalytic deoxyamination of readily available 2‐arylethanols offers an appealing, simple, and straightforward means of accessing β‐(hetero)arylethylamines of biological interest. Yet, it currently represents a great challenge to synthetic chemistry. In most cases, the alcohol has to be either pre‐activated in situ or converted into a reactive carbonyl intermediate, limiting the substrate scope for some methods. Examples of direct dehydrative amination of 2‐arylethanols are thus still scarce. Here, we describe a catalytic protocol based on the synergy of triflic acid and hexafluoroisopropanol, which enables the direct and stereospecific amination of a broad array of 2‐arylethanols, and does not require any pre‐activation of the alcohol. This approach yields high value‐added products incorporating sulfonamide, amide, urea, and aniline functionalities. In addition, this approach was applied to the sulfidation of 2‐arylethanols. Mechanistic experiments and DFT computations indicate the formation of phenonium ions as key intermediates in the reaction.
Fuel‐Driven π‐Conjugated Superstructures to Form Transient Conductive Hydrogels
Authors: Tsironi Ifigeneia , Maleszka Jarek A. , Kriebisch Brigitte A. K. , Wilson‐Kovacs Robert S. , Acevedo Orlando , O'Leary Shamus L. , Watt John , Boekhoven Job , Olivier Jean‐Hubert 
Published: October 2024

AbstractDespite advances in creating dissipative materials with transient properties, such as hydrogels and active droplets, their application remains confined to temporal changes in structural properties. Developing out‐of‐equilibrium materials whose electronic functions are parameterized by a chemical reaction cycle is challenging. Yet, this class of materials is required to construct biomimetic materials. In contrast to traditional chemical reaction cycles that exploit molecularly dissolved building blocks at thermodynamic equilibrium, we show that fiber structures derived from reactive naphthalene diimide (NDI) building blocks can be used as resting states to form far‐from‐equilibrium conductive hydrogels after the addition of chemical fuels. Upon fueling the NDI‐derived fibers, a dual‐component activation and deactivation pathway is deduced by kinetic analysis and is absent when using a molecularly dissolved resting state. Investigating the solid‐state morphologies of the structures formed throughout the fuel‐driven reaction cycle using cryo‐EM reveals that the resting thermodynamic fibers evolve to transient thicker fibrils and layered superstructures. We show that the transient redox‐active hydrogels exhibit a nearly threefold increase in electrical conductivity upon fuel consumption before reverting to their original value over hours. These far‐from‐equilibrium materials are potential candidates in applications such as programmable biorobotics and chemical computing.