bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pristine MXene: In Situ XRD Study of MAX Phase Etching with HCl+LiF Solution
Authors: Gurzęda Bartosz , Boulanger Nicolas , Nordenström Andreas , Dejoie Catherine , Talyzin Alexandr V. 
Published: October 2024

AbstractMany applications are suggested for Ti‐MXene motivating strong interest in studies of Ti3C2Tx synthesis by solution‐based methods. However, so far only ex situ studies of the synthesis are performed, mostly due to the difficulty of handling HF‐based solutions. Here the first time‐resolved in situ synchrotron radiation X‐ray Diffraction study of MXene synthesis performed using a plastic capillary‐size reaction cell directly in HF solution is reported. This study provides the first report on the structure of “pristine MXene” formed by Ti3AlC2 etching with LiF+HCl. The term “pristine” refers to the MXene structure found directly in HF solution. By comparing the interlayer distances of pristine MXene (≈13.5 Å), solvent‐free Li‐intercalated MXene (≈12.2 Å), and Li‐free MXene (≈10.7 Å), it can be concluded that the width of “slit pores” formed by terminated MX layers during the Al etching does not exceed ≈3 Å. The width of these slit pores is a key factor for HF etching of Al within the interlayers. This space constraint explains the slow kinetics of MXene formation in HF‐based synthesis methods. No intermediate phases are observed, suggesting that the crystalline MXene phase is formed by the simultaneous etching of Al and termination of Ti3C2 layers.
Targeted Analysis of Mitochondrial Protein Conformations and Interactions by Endogenous ROS‐Triggered Cross‐Linker Release
Authors: Zhou Wen , Chen Yuwan , Fu Wenxin , Li Xinwei , Xia Yufei , Zhao Qun , Zhao Baofeng , Zhang Yukui , Yang Kaiguang , Zhang Lihua 
Published: October 2024

AbstractThe study of in situ conformations and interactions of mitochondrial proteins plays a crucial role in understanding their biological functions. Current chemical cross‐linking mass spectrometry (CX‐MS) has difficulty in achieving in‐depth analysis of mitochondrial proteins for cells without genetic modification. Herein, this work develops the reactive oxygen species (ROS)‐responsive cross‐linker delivery nanoparticles (R‐CDNP) targeting mitochondria. R‐CDNP contains mitochondria‐targeting module triphenylphosphine, ROS‐responsive module thioketal, loading module poly(lactic‐co‐glycolic acid) (PLGA), and polyethylene glycol (PEG), and cross‐linker module disuccinimidyl suberate (DSS). After targeting mitochondria, ROS‐triggered cross‐linker release improves the cross‐linking coverage of mitochondria in situ. In total, this work identifies 2103 cross‐linked sites of 572 mitochondrial proteins in HepG2 cells. 1718 intra‐links reveal dynamic conformations involving chaperones with ATP‐dependent conformation cycles, and 385 inter‐links reveal dynamic interactions involving OXPHOS complexes and 27 pairs of possible potential interactions. These results signify that R‐CDNP can achieve dynamic conformation and interaction analysis of mitochondrial proteins in living cells, thereby contributing to a better understanding of their biological functions.
Multipoint Anionic Bridge: Asymmetric Solvation Structure Improves the Stability of Lithium‐Ion Batteries
Authors: Zheng Tianle , Xu Tonghui , Xiong Jianwei , Xie Weiping , Wu Mengqi , Yu Ying , Xu Zhuijun , Liang Yuxin , Liao Can , Dong Xiaoli , Xia Yongyao , Cheng Ya‐Jun , Xia Yonggao , Müller‐Buschbaum Peter 
Published: October 2024

AbstractIn this study, a novel concept of multipoint anionic bridge (MAB) is proposed and proved, which utilizes anions with different sites to connect with the asymmetric solvation structure (ASS). Compared to usual solvation structures, this study utilizes the multifunctional groups of difluoro(oxalate)borate anion (ODFB−), which can connect with Li+. By tailoring the concentration, the anion serves as a bridge between different solvated structures. The electrolyte is investigated through in situ techniques and simulations to draw correlations between different solvation structures and reaction pathways. The proposed design demonstrates remarkable high‐temperature performance on both the anode and cathode sides, enabling stable cycling of LCO||graphite (0.5 Ah, 1.0 C) pouch cell for over 200 cycles at 80 °C and facilitating Li||MCMB and Li||LFP cells to deliver stable performance for 200 cycles at 100 °C. This work paves the way for the development of high‐performance electrolyte systems by designing and using new multipoint anions to construct ASSs.
Ambient Moisture‐Induced Self Alignment of Polarization in Ferroelectric Hafnia
Authors: Wei Lu‐Qi , Guan Zhao , Tong Wen‐Yi , Fan Wen‐Cheng , Mattursun Abliz , Chen Bin‐Bin , Xiang Ping‐Hua , Han Genquan , Duan Chun‐Gang , Zhong Ni 
Published: October 2024

AbstractThe discovery of nanoscale ferroelectricity in hafnia (HfO2) has paved the way for next generation high‐density, non‐volatile devices. Although the surface conditions of nanoscale HfO2 present one of the fundamental mechanism origins, the impact of external environment on HfO2 ferroelectricity remains unknown. In this study, the deleterious effect of ambient moisture is examined on the stability of ferroelectricity using Hf0.5Zr0.5O2 (HZO) films as a model system. It is found that the development of an intrinsic electric field due to the adsorption of atmospheric water molecules onto the film's surface significantly impairs the properties of domain retention and polarization stability. Nonetheless, vacuum heating efficiently counteracts the adverse effects of water adsorption, which restores the symmetric electrical characteristics and polarization stability. This work furnishes a novel perspective on previous extensive studies, demonstrating significant impact of surface water on HfO2‐based ferroelectrics, and establishes the design paradigm for the future evolution of HfO2‐based multifunctional electronic devices.
SV2A PET shows hippocampal synaptic loss in cognitively unimpaired APOE ε4/ε4 homozygotes
Authors: Snellman Anniina , Tuisku Jouni , Koivumäki Mikko , Wahlroos Saara , Aarnio Richard , Rajander Johan , Karrasch Mira , Ekblad Laura L. , Rinne Juha O. 
Published: October 2024

AbstractINTRODUCTIONWe investigated hippocampal synaptic density using synaptic vesicle 2A positron emission tomography (PET), and its association with amyloid beta (Aβ) and cognitive performance in healthy apolipoprotein E (APOE) ε4 carriers.METHODSSynaptic density was assessed in 46 individuals (APOE ε4/ε4 n = 14; APOE ε3/ε4 n = 16; APOE ε3/ε3 n = 16) with [11C]UCB‐J‐PET standardized uptake value ratios (SUVRs), by using the centrum semiovale as a reference region. Differences in hippocampal [11C]UCB‐J SUVRs were analyzed with analysis of variance (ANOVA) and linear models. Associations among [11C]UCB‐J SUVR, Aβ, hippocampal volume, and cognitive variables were analyzed with Spearman correlation.RESULTSHippocampal synaptic density was different among the APOE groups (PANOVA = 0.016): APOE ε4/ε4 carriers had lower [11C]UCB‐J SUVRs compared to APOE ε3/ε3 (p = 0.013). Hippocampal synaptic density did not correlate with Consortium to Establish a Registry for Alzheimer's Disease (CERAD) total score (rho = −0.052, p = 0.74), Alzheimer's Prevention Initiative Preclinical Cognitive Composite (APCC) score (rho = 0.17, p = 0.28), or [11C]PiB uptake (rho = −0.10, p = 0.50).DISCUSSIONHippocampal synaptic loss emerges early in the AD continuum and is measurable in vivo in cognitively unimpaired high‐risk individuals.Highlights
Synaptic density was studied in vivo in healthy older adults using [11C]UCB‐J positron emission tomography.
Apolipoprotein E (APOE) ε4/ε4 carriers had lower hippocampal synaptic density compared to APOE ε3/ε3.
Synaptic density was not associated with cognitive performance in this population.
Hippocampal synaptic alterations occur before clinical symptoms in APOE ε4/ε4 carriers.
Directional Subthalamic Deep Brain Stimulation Better Improves Gait and Balance Disorders in Parkinson's Disease Patients: A Randomized Controlled Study
Authors: Cherif Saoussen , Tempier Nicolas , Yeche Mathieu , Temiz Gizem , Perrière Julia , Romanato Marco , Ziri Déborah , Fernandez‐Vidal Sara , Hainque Elodie , Maltête David , Derrey Stéphane , Bardinet Eric , Lau Brian , Karachi Carine , Welter Marie‐Laure 
Published: October 2024

ObjectiveTo investigate the effects of directional subthalamic deep brain stimulation (STN‐dDBS) on gait and balance disorders, including freezing of gait (FOG), in patients with advanced Parkinson's disease (PD).MethodsWe included 10 participants who underwent STN‐DBS and presented severe preoperative FOG, in a randomized, double‐blind, crossover study. We used segmented DBS electrodes to investigate whether directing the predicted volume of tissue activated (VTA) to overlap the central STN preferentially improved gait and balance disorders compared to directional DBS applied in the more posterior STN (sensorimotor). We also assessed non‐directional (ring‐mode) STN‐DBS. Our primary outcome was gait and balance control measured using instrumented gait recordings. Each patient had a pre‐operative structural and diffusion‐weighted imaging to model individual VTAs and to examine cortico‐subthalamic connectivity. We used linear mixed‐effects models to contrast the effects of central STN‐dDBS, posterior STN‐dDBS, and ring‐mode STN‐DBS.ResultsCentral STN‐dDBS produced significantly better improvement in gait and balance control compared to posterior STN‐dDBS (p = 0.027), with fewer FOG episodes (p < 0.001). Conversely, ring‐mode STN‐DBS resulted in worsened postural control compared to central STN‐dDBS (p = 0.009). The cortico‐subthalamic connectivity with the STN VTAs involved mostly primary sensorimotor, premotor, and medial frontal cortices, with a higher overall cortico‐STN connectivity with ring‐mode STN‐DBS.InterpretationCentral STN‐dDBS represents the best option to improve gait and balance disorders in PD patients, including FOG. Our findings raise the possibility of reprogramming STN‐DBS toward the central area in selected patients with disabling FOG and/or postural instability after surgery. ANN NEUROL 2025;97:149–162
Association of Seizure Control with Mortality, Cognition, and Function in People With Dementia
Authors: Zawar Ifrah , Quigg Mark , Ghosal Soutik , Punia Vineet , Calle‐Lopez Yamile , Manning Carol , Kapur Jaideep 
Published: October 2024

ObjectivesThe effects of seizure control on outcomes in persons with dementia (PWD) remain unclear. Our study aimed to investigate the impact of seizure control on mortality, function, cognition, and mood among PWD.MethodsThis longitudinal, multicenter study is based on 39 Alzheimer's disease centers (ADCs) in the United States from September 2005 to December 2021. PWD were grouped by seizure status into recurrent (seizures in the past year), remote (prior seizures but none in the past year), and no seizures (controls). The primary outcome was all‐cause mortality among seizure groups. We used Weibull survival analysis to assess the mortality risks by seizure status after adjusting for age, sex, education, race, ethnicity, hypertension, diabetes, hyperlipidemia, degree of cognitive impairment, dominant Alzheimer's disease (AD) mutation, brain trauma, stroke, Parkinson's disease, alcohol abuse, and depression. Cognition (Clinical Dementia Rating), function (physical dependence and nursing home residence), day‐to‐day activities (Functional Assessment Scores), and mood (Geriatric Depression Scale) were compared among seizure groups after adjusting for dementia duration and age.ResultsAmong 26,501 participants, 374 (1.4%) had recurrent seizures and 510 (1.9%) had remote seizures. In multivariable survival analysis, recurrent seizures were associated with a higher mortality risk than remote and no seizures (adjusted hazard ratio [aHR], 95% confidence interval [95% CI]; recurrent aHR = 1.79, 95% CI = 1.51 to 2.12; remote aHR = 1.17, 95% CI = 0.98 to 1.38). Median time‐to‐death for recurrent, remote, and no seizures was 2.4, 4.0, and 4.7 years, respectively. People with recurrent seizures had worse cognition, day‐to‐day function, and physical dependence than those with remote seizures and controls.InterpretationPWD with poorly controlled recurrent seizures have worse mortality, functional, and cognitive outcomes than PWD with remote and no seizures. These findings underscore the need for timely identification and management of ongoing seizures in PWD. ANN NEUROL 2025;97:358–368
Calcium Carbonate as an Ionic Molecular Lock for Ultrastrong Fluorescence of Single Organic Molecules
Authors: Zhang Jian , Xu Hengyue , Fang Weifeng , Liu Xin , Zhang Haoke , Tang Ruikang , Liu Zhaoming 
Published: October 2024

AbstractLocking molecular conformation are widely applied in molecular engineering for improved performance. However, locking via organic functional groups often changes the original molecular properties. Following the rigidity and stability of ionic interaction in ionic compounds, we suggested the use of a molecular‐scale ionic compound, calcium carbonate oligomer, as a robust molecular segment to functionalize organic molecules. The rigid structure of the ionic molecular segments locked the organic molecules, which could remarkably limit the intramolecular motion and intermolecular interactions. This ensured a stable and ultrastrong fluorescence of the single organic molecule while preserving its original maximum emission wavelength. The locking strategy was general and extendable to multiple organic molecules. Additionally, the ultrastrong single‐molecular fluorescence can be maintained in inorganic solids with even higher quantum yields and almost unchanged maximum emission wavelength. The highest quantum yield of the investigated molecules reached 99.9 %, superior to all reported organic‐inorganic fluorescent composite under air conditions. This work demonstrates a general strategy to restrict intramolecular motion and intermolecular interactions by using ionic oligomers as molecular locks, providing an alternative method for realizing ultraemissive molecules. This further demonstrates a fascinating example of molecular engineering in the presence of inorganic ionic molecules.
Polar Order in a Fluid Like Ferroelectric with a Tilted Lamellar Structure – Observation of a Polar Smectic C (SmCP) Phase
Authors: Hobbs Jordan , Gibb Calum J. , Pociecha Damian , Szydłowska Jadwiga , Górecka Ewa , Mandle Richard J. 
Published: October 2024

AbstractThe discovery of fluid states of matter with spontaneous bulk polar order is appreciated as a major discovery in the fields of soft matter and liquid crystals. Typically, this manifests as polar order superimposed atop conventional phase structures and is thus far limited to orthogonal phase types. Here we report a family of materials which exhibit a previously unseen state of matter which we conclude is a polar smectic C phase, and so we term it SmCP. The spontaneous polarisation of the SmCP phase is over two orders of magnitude larger than that found in conventional ferroelectric SmC phase of chiral materials used in some LCD devices. Fully atomistic molecular dynamics simulations faithfully and spontaneously reproduce the proposed structure and associated bulk properties; comparison of experimental and simulated X‐ray scattering patterns shows excellent agreement. The materials disclosed here have significantly smaller dipole moments than typical polar liquid crystals such as RM734 which suggests the role of molecular electrical polarity in generating polar order is perhaps overstated, a view supported by consideration of other molecular systems.
Interweavable Metalloporphyrin‐Based Fibers for Indirect Electrocatalysis
Authors: Yao Xiaoman , Liu Gang , Huang Yingying , Huang Caier , Chen Xuanxu , Xuan Zhe , Shi Mingjin , Yang Yiwen , Huang Xianqiang , Chen Yifa , Lan Ya‐Qian 
Published: October 2024

AbstractThe applications of indirect electrocatalysis toward potential industrial processes are drastically limited by the utilization or processing forms of electrocatalysts. The remaining challenges of electrocatalysts like the recycling in homogeneous systems or pulverization in heterogeneous systems call for advanced processing forms to meet the desired requirements. Here, we report a series of metalloporphyrin‐based polymer fibers (M−PF, M=Ni, Cu and Zn) through a rigid‐flexible polymerization strategy based on rigid metalloporphyrin and flexible thiourea units that can be applied as heterogeneous redox‐mediators in indirect electrocatalysis. These functional fibers with high strength and flexibility exhibit interweavable and designable functions that can be processed into different fiber‐forms like knotted, two‐spiral, three‐ply, five‐ply fibers or even interweaved networks. Interestingly, they can be readily applied in S−S bond cleaving/cyclization reaction or extended oxidative self‐coupling reaction of thiols with high efficiency. Remarkably, it enables the scale‐up production (1.25 g in a batch‐experiment) under laboratory conditions.
Sulfur‐Rich Norbornadiene‐Derived Infrared Transparent Polymers by Inverse Vulcanization
Authors: Wuliu Yishun , Dong Weiliang , Huang Guohua , Xie Hui , Yao Pingping , Tan Jiji , Mu Kexin , Zhang Zhili , Chen Yinan , Wang Mingliang , Tian Lei , Zhu Caizhen , Xu Jian 
Published: October 2024

AbstractInfrared (IR) transparent polymer materials prepared by inverse vulcanization, as a promising candidate to replace inorganic materials, are new materials for constructing key devices in IR optics. However, it is difficult to achieve a balance between infrared optical and thermal properties in polymers due to the intrinsic infrared absorption of organic materials. Herein, our strategy is to construct a high boiling point symmetrical molecular norbornadiene derivative cross‐linking agent (DMMD) which can be inverse vulcanized with molten sulfur, and obtain Poly (S‐r‐DMMD) with different sulfur content by controlling the feed ratio of sulfur. With the rigid core and low IR activity in DMMD, the prepared polymers exhibit tunable thermal properties (Tg: 98.3–119.8 °C) and high IR transmittance (medium‐wave infrared region (MWIR): 42.9–52.6 %; long‐wave infrared region (LWIR): 1.5–5.29 %). In addition, Poly (S‐r‐DMMD) can be used to prepare large‐size free‐standing Fresnel lenses for IR imaging by simple hot‐pressing, which provides flexibility in the design and production of IR fine lenses. This study provides a novel strategy for balancing the thermal and optical properties of IR transparent polymer materials, while providing relevant references for balancing the IR optical and thermal properties of polymer materials.
Enhanced Quantum Efficiency via Co‐Substitution in Red‐Emitting Phosphor Sr2[MgAl5N7] : Eu2+ for Advanced Spectroscopic Applications Including Laser Displays with Ultra‐High Luminescence Saturation Threshold
Authors: Li Zebin , Wang Haoyang , Su Zhezhe , Kang Runtian , Seto Takatoshi , Wang Yuhua 
Published: October 2024

AbstractIn order to obtain novel and more efficient red light‐emitting materials, a series of Sr2[Mg1−xLixAl5−xSixN7] : 0.01Eu2+ (SMAN‐xLS, 0≤x≤0.5) red phosphors were devised and successfully synthesized via the high temperature solid state reaction and the effects of the co‐substitution of [Mg−Al]5+ by [Li−Si]5+ on structural and luminescence properties is investigated in detail. A series of powder XRD data and Rietveld refinement indicate that [Li−Si]5+ co‐substitution can successfully enter the Sr2[MgAl5N7] : 0.01Eu2+ (SMAN) lattice. With the entry of [Li−Si]5+ into the lattice, the substitution of Al3+ by Si4+ leads to the weakening of the nephelauxetic effect of the 5d level of Eu2+, which shifts the emission peak from 657 nm to 647 nm and reduces the excitation in the green region, i.e., lowers the absorption of green light. When the amount of [Li−Si]5+ co‐substitution is x=0.1, the luminescence intensity and thermal stability of the sample are enhanced, in which the external quantum efficiency (EQE), reflecting the luminescence intensity, is elevated by 49.6 %. The increase in lattice rigidity gives rise to higher luminescence intensity, and the introduced trap levels for the compensation of luminescence enhances the thermal stability. Under blue laser excitation, the SMAN‐0.1LS can achieve an ultra‐high luminescence saturation threshold of 52.22 W/mm2, which is remarkably superior to other existing red phosphors, a breakthrough performance that has enormous potential for application in high‐power laser display light sources. Cathodoluminescence (CL) characterization and measurements attest to the favorable CL properties of SMAN‐0.1LS. By measuring the pressure‐dependent luminescence of SMAN‐0.1LS, the emission peak can be shifted from 650 nm to 702 nm with the increase of pressure, and the sensitivity dλ/dP is 5.07 nm/GPa, which is indicative of the potential application of this system as an optical pressure sensor.
Stabilization of Ethane‐Like Dianionic Diborane(6) in Monometallic Titanium Complexes and its Subsequent B(sp3)−B(sp3) Bond Cleavage
Authors: Bairagi Subhash , Giri Soumen , Joshi Gaurav , Jemmis Eluvathingal D. , Ghosh Sundargopal 
Published: October 2024

AbstractTreatment of [Cp*TiCl3] with [LiBH4 ⋅ THF] followed by thermolysis with [Ph2E2] (E=S or Se) resulted in the formation of classical diborane(6) complexes, [(Cp*Ti)(η4‐B2H4LL′)] (L=C6H4E; L′=C6H5E; 1 a: E=S, 1 b: E=Se), stabilized at titanium template. To the best of our knowledge, they are the first examples of mono‐metallic classical diborane(6) complexes. The bonding analysis and theoretical studies suggest that the stabilization of these diborane(6) species is due to the presence of four bridging ligands in ĸ4‐fashion, where two of them are phenyl thiolates/selenolates that provide more electrons to the electron‐deficient titanium center. Reactions of these diborane(6) species with [M(CO)5 ⋅ THF] (M=Mo, W) led to the cleavage of the electron‐precise B(sp3)−B(sp3) bond that yielded ĸ3‐hydridoborato complexes [(Cp*Ti)(ĸ3‐BH3R)(μ‐EPh)2{M(CO)4}] (2 a–c: R=H, 3 a–c: R=Ph). In an attempt to isolate the Te‐analogue of 1 a–b, a similar reaction was performed; however, the complex was too unstable to be isolated. Interestingly, the treatment of this unstable intermediate with [W(CO)5 ⋅ THF] yielded [(Cp*Ti)(ĸ3‐BH3R)(μ‐TePh)2{W(CO)4}] (2 d: R=H, 3 d: R=Ph) that are analogues of 2 a–c and 3 a–c, respectively. Formation of these species provide indirect evidence for the existence of unstable [(Cp*Ti)(η4‐B2H4LL′)] (L=C6H4Te; L′=C6H5Te; 1 c).
Multidentate Chelating Ligands Enable High‐Performance Zinc‐Bromine Flow Batteries
Authors: Xia Weicheng , Xie Kunchi , Gao Shang , Song Zhen , Chen Long , Li Chunzhong 
Published: October 2024

AbstractZinc bromine flow battery (ZBFB) is a promising battery technology for stationary energy storage. However, challenges specific to zinc anodes must be resolved, including zinc dendritic growth, hydrogen evolution reaction, and the occurrence of “dead zinc”. Traditional additives suppress side reactions and zinc dendrite formation by altering the solvation structure of Zn2+ and adsorbing onto the zinc surface through only a limited number of zincophilic sites, resulting in weak adsorption on zinc metal and potential inability to simultaneously optimize the solvation structure of zinc ions. Obviously, increasing the number of potential zincophilic sites in the additive can significantly enhance the interaction with zinc. Herein, we propose a strong chelate, ethylenediamine tetramethylene phosphonic acid (EDTMPA) as the additive, which boasts six potent zincophilic sites, not only promotes the formation of the water‐deficient inner Helmholtz plane but also plays a crucial role in restructuring the solvation environment of Zn2+. As a result, the zinc symmetric flow battery with EDTMPA exhibited exceptional coulombic efficiency of 99.4 % over 800 cycles, surpassing the previous studies by a significant margin. Furthermore, the assembled ZBFB has showcased a dendrite‐free and enduring cycling over 400 cycles at 80 mA cm−2.