bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chlorine Axial Coordination Activated Lanthanum Single Atoms for Efficient Oxygen Electroreduction with Maximum Utilization
Authors: Yin Leilei , Sun Mingzi , Zhang Shuai , Huang Yongkang , Huang Bolong , Du Yaping 
Published: December 2024

AbstractCurrently, there are still obstacles to rationally designing the ligand fields to activate rare‐earth (RE) elements with satisfactory intrinsic electrocatalytic reactivity. Herein, axial coordination strategies and nanostructure design are applied for the construction of La single atoms (La‐Cl SAs/NHPC) with satisfactory oxygen reduction reaction (ORR) activity. The nontrivial LaN4Cl2 motifs configuration and the hierarchical porous carbon substrate that facilitates maximized metal atom utilization ensure high half‐wave potential (0.91 V) and significant robustness in alkaline media. The aqueous and flexible Zinc‐air battery (ZAB) integrating La‐Cl SAs/NHPC as the cathode catalyst exhibits a maximum power density of 260.7 and 68.5 mW cm−2, representing one of the most impressive RE‐based ORR electrocatalysts to date. Theoretical calculations have demonstrated that the Cl coordination evidently modulate the electronic structures of La sites, which promoted electron transfer efficiency by d‐p orbital couplings. With enhanced electroactivity of La sites, the adsorptions of key intermediates are optimized to alleviate the energy barriers of the potential‐determining step. Importantly, this preparation strategy is also successfully applied to other REs. This work provides perspectives for near‐range electronic structure modulation of RE‐SAs based on a nonplanar coordination micro‐environment for efficient electrocatalysis.
Wrinkling of Quasi‐2D Perovskite for High‐Performance and Flexible Photodetectors
Authors: Lei Sanfeng , He Zhenmei , Hu Chenyu , Zhang Guoshuai , Zhu Xixiang , Li Jinpeng , Wang Kai , Yu Haomiao 
Published: December 2024

AbstractFlexible photodetectors have garnered significant attention in recent years due to their potential applications in emerging fields such as artificial intelligence, medical diagnostics, and wearable devices. Quasi‐2D perovskites exhibit remarkable optoelectronic properties, excellent environmental stability, and mechanical flexibility, making them promising materials for flexible photodetectors. Achieving precise control over the morphology of these materials is crucial for enhancing device performance. In this study, periodic wrinkle structures are introduced into quasi‐2D perovskite films by applying pre‐stretching stress to a flexible substrate. These results indicate that these ordered wrinkle structures facilitate grain movement during formation, enabling smaller grains to fill pores and surround larger grains. This process leads to a denser film with a mixed 2D‐3D phase architecture, enhancing charge transfer efficiency and prolonging carrier lifetime in the perovskite films. Consequently, the responsivity of the resulting flexible perovskite photodetector significantly increased, reaching 86.7 A W−1, which is 2.5 times higher than that of the unstretched device. Furthermore, the wrinkled structures enhanced mechanical tolerance, allowing the photodetector to retain 80% of its initial responsivity even after 10 000 stretching cycles. These findings highlight the potential of wrinkled structures to significantly enhance the performance of flexible perovskite optoelectronic devices.
Targeting ACAT1 for Precision Chemo‐Immunoprevention in Lung Cancer
Authors: Huang Mofei , Pan Jing , Sei Shizuko , Wang Yian , You Ming 
Published: December 2024

AbstractLung cancer (LC) is a leading cause of cancer‐related deathworldwide, and altered cholesterol metabolism is a hallmark of cancer cells. Acyl‐CoA:cholesterol acyltransferase 1(ACAT1), or Sterol O‐acyltransferase 1 (SOAT1), isa key cholesterol esterification enzyme. Its overexpression promotes tumorprogression by accumulating cholesterol esters. Inhibition of ACAT1 also potentiatesCD8+ T cells medicated anti‐tumor immunity by increasing plasma membranecholesterol level. This study, as the first of its kind, shows the ACAT1/SOAT1 overexpressioncorrelates with poor prognosis in early‐stage lung adenocarcinoma (LUAD) patients.Long‐term treatment with ACAT1 inhibitor avasimibe suppresses tumorigenesis inboth Kirsten rat sarcoma viral oncogene homolog (KRAS) and epidermal growthfactor receptor (EGFR) mutation‐induced LC mouse models without overttoxicity. ACAT1 inhibition reduces tumor cell proliferation, migration, andinvasion and causes G0/G1 cell cycle arrest, while boosting CD8+ T cells'effector function and memory phenotype. Single‐cell RNA sequencing reveals thatACAT1 inhibition downregulates cholesterol biosynthesis and central carbon andnitrogen metabolism pathways in tumor cells, while upregulating genes relatedto oxidative phosphorylation and fatty acid oxidation in CD8+ T cells. Finally, avasimibe improves the efficacy of a human EGFR vaccine in preventing LCprogression. These novel findings suggest potential strategies for cancer preventionand therapy.
Flexible X‐Ray Detector for Cumulative Dose Monitoring Through Reversible Photochromism and Luminescence Modulation
Authors: Bai Xue , Zhang Yueteng , Zhao Heping , Zi Yingzhu , Xu Zan , Huang Anjun , Cun Yangke , Liu Yue , Song Zhiguo , Qiu Jianbei , Liao Jiayan , Yang Zhengwen 
Published: December 2024

AbstractThis study presents a multi‐mode X‐ray detection and imaging strategy by integrating photochromism, photoluminescence, and radioluminescence into Tb3+‐doped CaAl2Si2O8. CaAl2Si2O8: Tb3+ exhibits stable radioluminescence, oxygen vacancy‐related photochromism, and photoluminescence modulation, all of which showed a linear relationship with X‐ray exposure. This multi‐mode response enables high‐quality imaging and detection in both bright and dark conditions, facilitating time‐dependent cumulative X‐ray radiation dose assessments. Reversible color and luminescence changes are achieved through cyclic tests involving alternating X‐ray and 473 nm laser irradiation. The PDMS CaAl2Si2O8: Tb3+ ink and flexible film demonstrate high suitability for wearable X‐ray detection devices and imaging of irregular objects, offering an innovative approach to X‐ray detection and imaging.
Compositional Gradient of Mixed Halide 2D Perovskite Interface Boosts Outdoor Stability of Highly Efficient Perovskite Solar Cells
Authors: Degani Matteo , Pallotta Riccardo , Pica Giovanni , Karimipour Masoud , Mirabelli Alessandro , Frohna Kyle , Anaya Miguel , Xu Tianyu , Ma Chang‐Qi , Stranks Samuel D. , Cantù Monica Lira , Grancini Giulia 
Published: December 2024

AbstractInterface engineering using self‐assembled 2D perovskite interfaces is a consolidated route to efficient and durable perovskite solar cells. Whether the 2D perovskite forms a homogeneous conformal layer or is heterogeneously distributed on the surface, interface defects are passivated, leading to a general improvement in the device's open circuit voltage (VOC) and stability. Here, an innovative strategy is developed for manipulating the composition of the 2D/3D perovskite interface that results in the formation of a gradient halide distribution, which extends from the surface to the bulk. The use of a bromide‐based 2D perovskite triggers a progressive Br/I exchange, affecting not only the surface but also the perovskite underneath. As a result, not only the device VOC improve, as expected, but also the photogenerated current is boosted, leading to a device efficiency of up to 24.4%. Such mixed halide gradient effectively passivates surface and bulk defects making the perovskite active layer more efficient and robust, as demonstrated by the superior device stability showing zero losses in performances upon 36 days (more than 800 h) test in outdoor conditions, those ones relevant for a marketable product.
Charge Storage Mechanisms in Batteries and Capacitors: A Perspective of the Electrochemical Interface
Authors: Ghasemiahangarani Parham , Farhan Gabriel , del Mundo Donovan , Schoetz Theresa 
Published: December 2024

AbstractResearchers developing the next generation of energy storage systems are challenged to understand and analyze the different charge storage mechanisms, and subsequently use this understanding to design and control materials and devices that bridge the gap between high specific energy and power at a target cycle life. Correctly identifying and quantifying the prominent charge storage mechanism is of the utmost importance for understanding how the system functions and tuning material properties for specific applications. The different charge storage mechanisms are defined by a characteristic current‐time scaling that has been defined for electrochemical interfaces with faradaic diffusion‐limited charge storage. However, the characteristic current‐time scaling for faradaic non‐diffusion‐limited (or pseudocapacitive) charge storage remains unelucidated despite to date many battery types, particularly those having 2D electrode materials and electrolytes with ionic liquids, deep eutectic solvents, or highly concentrated electrolytes, exhibit electrochemical interfaces with pseudocapacitive charge storage. This perspective discusses the necessary mathematical expressions and theoretical frameworks for all charge storage mechanisms which are corroborated with experimental data. This perspective can be used as a guide to quantitatively disentangle and correctly identify charge storage mechanisms and to design electrochemical interfaces and materials with targeted performance metrics for a multitude of electrochemical devices.
Engineering Ultrafast Photo‐Induced Charge and Carbon Intermediates Transfer at Interface to Break the Activity‐Selectivity Trade‐Off in Direct Conversion of Methane to Methanol
Authors: Cao Yuehan , Yu Wang , Li Yi , Meng Jie , Zheng Kaibo , Huang Chuan , Yang Xin , Yang Yuantao , Dong Fan , Zhou Ying 
Published: December 2024

AbstractDirectly converting methane to methanol with solar light and eco‐friendly oxidants is challenging due to single‐step conversion process where the designed active sites commonly cleave C─H bonds in both methane and methanol. Herein, a novel method is proposed to break activity‐selectivity trade‐off in methane conversion to methanol through interface engineering. Taking BiOI/BN as a proof‐of‐concept model, it's discovered that engineered interface provides distinct active sites for methane activation and overoxidation products photoreduction. Based on in situ infrared spectroscopy, ultrafast laser spectroscopy, and theoretical calculations, it is unlocked that the engineered interface induces the passivation of original trap states in BiOI component, greatly hindering ultrafast trap‐mediated recombination of photo‐induced carriers (≈39.7 ps). Benefiting from it, long‐lived electrons could directly participate in active radicals generation, ensuring effective methane activation. Subsequently, overoxidation carbon intermediates and protons are captured by active sites from the BN component and rapidly accumulated on the surface. This enables effective injection of electrons into bonding orbitals of C─H bonds in methanol, accelerating the occurrence of C─H re‐bonding process. Ultrafast photo‐induced charge and carbon intermediates transfer at interfaces results in high methane conversion rate of 15.5% under atmospheric pressure and maintains methanol selectivity of 86.4% for 24 h long‐time reaction process.
Coordinated Na+ Diffusion and Multiscale Interfacial Engineering of Polymer Electrolyte for Room‐Temperature Solid Sodium Metal Batteries
Authors: Guo Yuxiang , Liu Jiacheng , Shao Ahu , Cheng Lu , Tang Jiawen , Zhang Yaxin , Wang Zhiqiao , Li Yunsong , Wang Yingche , Wang Helin , Li Chunwei , Liu Ting , Zhao Xiaodong , Ma Yue 
Published: December 2024

AbstractThin‐layer composite polymer electrolytes (CPEs) provide a safer alternative to flammable liquid electrolytes for all‐solid‐state sodium metallic batteries (ASSMBs) prototyping. However, conventional CPE designs suffer from insufficient ionic conductivities, oxidation upon high‐voltage and uncontrolled dendrite growth. Herein, an interpenetrating approach by incorporating an optimized amount of acrylamide (AM) monomers polymerized within polyethylene oxide (PEO) matrix is proposed. The amide groups within tangled PEO/poly(acrylamide) (PAM) segments facilitate the NaTFSI salt dissociation through the coordination between CO═Na+ and N─H/TFSI− interactions, meanwhile boosting Na+ conduction along the ethylene oxide chains. Integrated with bacterial cellulose scaffold for mechanical reinforcement, the CPE membrane reconciles the tensile strength, ionic conductance and transference number. Robotic‐arm controlled spray coating applies 4,4′‐(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 1,2‐dibromobenzene (1,2‐DBB) onto opposite sides of the PEO/PAM‐BC membrane. The electron‐withdrawing 6FDA layer promotes a NaF‐rich cathode interface with 4.74 V tolerance, while the electron‐accepting 1,2‐DBB creates a NaBr‐rich layer that mitigates the Na+ diffusion barrier. In the ASSMB configuration, the prototype demonstrates 85.4% capacity retention over 500 cycles at room‐temperature and wide‐temperature‐range adaptability from 0 to 80 °C. Transmission‐mode X‐ray diffraction reveals reversible lattice breathing of the paired cathode, which highlights the synergistic Na diffusion and stabilized interfaces across scales for the practical CPE design.
Synthesis of N‐,O‐,S‐Heterocyclic Spiroadamantanes by Condensation of Ketones with Bifunctional OH‐, NH‐, SH‐Acids under the Action of Copper‐Containing Catalysts
Authors: Gallyamova Leysan I. , Bayguzina Alfiya R. , Ramazanov Ilfir R. 
Published: December 2024

AbstractSynthesis of adamantyl‐containing cyclic ketals, spirooxazolidines, spiroimidazolidines, spirooxathiolanes, spirodithiolanes, spirooxazines, spirobenzodioxoles with high yields was carried out by condensation of adamantyl‐containing ketones (adamantanone, kemantan, diamantanone) with diols, 1,2‐ethanedithiol and 2‐mercaptoethanol, 1,2‐diaminoethane and 2‐aminoethanol under the action of copper‐containing catalysts. In the case of multigram‐scale reaction of adamant‐2‐one with 1,2‐propanediol, the amount of catalyst can be reduced to 0.1 mol %.
Visible‐Light Mediated, Photocatalyst‐Free C−S Bond Formation via EDA Complex Formation
Authors: Shanthi. Markabandhu , Perumal Karuppaiah , Hemamalini Vijayakumar , Dandela Rambabu , Ramesh Subburethinam 
Published: December 2024

AbstractThe presence of sulphur groups in the structures of many natural products and therapeutic candidates makes sulfur‐containing molecules indispensable. In organic chemistry, the study of carbon‐sulfur (C−S) bond formation via electron donor‐acceptor (EDA) complexes is a dynamic and developing field. EDA complexes facilitate a variety of chemical transformations, including the production of C−S bonds, by interacting between an electron‐rich donor and an electron‐deficient acceptor. In this review, we focus on the literature reports on formation of electron donor‐acceptor complex (EDA) between appropriate starting materials. Some new research investigates the use of light to stimulate C−S bond formation using EDA complexes. Photo‐redox catalysis is a promising field in which substrates can be activated under gentler circumstances. In this review, we have highlighted the photoactivation of the EDA complex and an intermediate formed in the reaction itself. We classified the collection of the journal under the following headings such as one pot ring annulation and cyclization involving C−S bond formation, C−S bond formation by dehalogenation, C−S bond formation in multicomponent reaction, C−S bond formation by leaving group, C−S bond formation on alkene/alkyne and other miscellaneous.
A Practical Approach to Cyclopropanation of Masked o‐Benzoquinones with Applications in Tropolone Derivative Synthesis
Authors: Huang Kuan‐Hsun , Lo Yao‐Ping , Mukherjee Anupam , Devendar Badugu , Sharma Sandeep , Chiu I.‐Chen , Chang Yu‐Pei , Chang Yi‐Chuan , Wu Chi‐Phi , Liao Chun‐Chen , Chuang Gary Jing 
Published: December 2024

AbstractThe Corey–Chaykovsky cyclopropanation of readily available masked o‐benzoquinones (MOBs) has been investigated to generate functionalized bicyclo[4.1.0]heptane derivatives with regioselectivity. The resulting bicyclic products were subjected to a sequence of hydrolysis, BF₃ ⋅ Et₂O‐mediated ring‐opening, and then again hydrolysis to access various tropolone derivatives – a class of molecules with significant roles in synthetic, biological, and theoretical chemistry. Utilizing an improved approach based on established cyclopropanation and ring‐opening strategies, several bicyclo[4.1.0]heptanes, tropolone difluorides, and tropolones can be synthesized from readily available MOBs. Our efforts focused on modifying each step to make these reactions general and of considerable practical value.
Lewy body co‐pathology in Alzheimer's disease and primary age‐related tauopathy contributes to differential neuropathological, cognitive, and brain atrophy patterns
Authors: Almeida Francisco C. , Santos Alexandra , Jesus Tiago , Coelho Ana , Quintas‐Neves Miguel , Gauthreaux Kathryn , Mock Charles N. , Kukull Walter A. , Crary John F. , Oliveira Tiago Gil 
Published: December 2024

AbstractINTRODUCTIONAlzheimer's disease (AD) co‐pathology with Lewy bodies (LB) is frequent and influences clinical manifestations and outcomes. Its significance in primary age‐related tauopathy (PART) is unknown. We investigated the influence of LB on cognition and brain atrophy in AD and PART.METHODSWe performed a retrospective cohort study in a large sample of autopsied participants with AD neuropathological change (ADNC) with and without LB and PART with and without LB, with corresponding ante mortem magnetic resonance imaging (MRI) data from the National Alzheimer's Coordinating Center dataset.RESULTSLB co‐pathology worsened cognitive impairment in both PART and ADNC. On longitudinal follow‐up, LB impacted cognitive decline in multiple domains. Additionally, LB influenced brain atrophy on MRI across groups and LB regional staging was different in PART and ADNC, accompanying tauopathy progression.DISCUSSIONThese results suggest that LB co‐pathology is associated with divergent patterns of cognitive impairment, brain atrophy, and regional pathological distribution in PART and AD.Highlights
Lewy body (LB) co‐pathology is frequent in Alzheimer's disease (AD) with important clinical implications.
LB co‐pathology is also present in primary age‐related tauopathy (PART), but its significance is still understudied.
In PART and AD, LB leads to higher cognitive impairment and brain regional atrophy.
In PART and AD, LB tends to accompany neurofibrillary tangle progression, suggesting amyloid pathology might be a trigger for regional pathology progression.
Differential associations of neighborhood disadvantage, race/ethnicity, and cognitive status with experiences of psychosocial distress in the HABS‐HD cohort
Authors: Rhoads Tasha , Wong Christina G. , Cobos Kimberly , O'Bryant Sid E. , Kind Amy J. H. , Miller Justin B. ,   Health and Aging Brain Study (HABS‐HD) Team
Published: December 2024

AbstractINTRODUCTIONUnderstanding how contextual socioeconomic factors are associated with psychosocial distress among different ethnoracial groups is important for addressing health disparities in individuals at risk for Alzheimer's disease.METHODSUsing Health and Aging Brain Study–Health Disparities (HABS‐HD) data collected between 2017 and 2023, we examined the association of neighborhood disadvantage with psychosocial distress using demographically adjusted linear regression models, stratified by ethnoracial group and cognitive status.RESULTSWe included 630 non‐Hispanic Black, 1109 Hispanic, and 1068 non‐Hispanic White older adults deemed cognitively normal (CN) or diagnosed with mild cognitive impairment (MCI). Residing in areas of greater neighborhood disadvantage was associated with increased chronic stress (CS) among CN White participants, but this relationship was attenuated among White participants with MCI. Regardless of cognitive status, severe levels of disadvantage were associated with increased CS and depression among Black participants.DISCUSSIONAging in more disadvantaged neighborhoods was associated with greater CS and depression for Black and White participants.Highlights
Greater neighborhood disadvantage was associated with increased depression and chronic stress for White and Black individuals.
Individuals with mild cognitive impairment reported greater levels of psychosocial distress.
These findings are relevant for addressing mental health inequity in aging populations.
Association of APOE alleles and polygenic profiles comprising APOE‐TOMM40‐APOC1 variants with Alzheimer's disease neuroimaging markers
Authors: Kulminski Alexander M. , Jain‐Washburn Ethan , Nazarian Alireza , Wilkins Heather M. , Veatch Olivia , Swerdlow Russell H. , Honea Robyn A. 
Published: December 2024

AbstractINTRODUCTIONTOMM40 and APOC1 variants can modulate the APOE‐ε4‐related Alzheimer's disease (AD) risk by up to fourfold. We aim to investigate whether the genetic modulation of ε4‐related AD risk is reflected in brain morphology.METHODSWe tested whether 27 magnetic resonance imaging‐derived neuroimaging markers of neurodegeneration (volume and thickness in temporo‐limbic regions) are associated with APOE‐TOMM40‐APOC1 polygenic profiles using the National Alzheimer's Coordinating Center Uniform Data Set linked to the AD Genetic Consortium data.RESULTSAll brain regions studied using structural phenotypes were smaller in individuals with AD. The ε4 allele was associated with smaller limbic (entorhinal, hippocampus, parahippocampus) brain volume and cortical thickness in AD cases than controls. There were significant differences in the associations for the higher‐risk and lower‐risk ε4‐bearing APOE‐TOMM40‐APOC1 profiles with temporo‐limbic region markers.DISCUSSIONThe APOE‐AD heterogeneity may be partly attributed to the modulating role of the TOMM40 and APOC1 genes in the APOE cluster.Highlights
The ε4 allele is associated with smaller values of neuroimaging markers in AD cases.
Larger values of neuroimaging markers may protect against AD in the ε4 carriers.
TOMM40 and APOC1 variants differentiate AD risk in the ε4 carriers.
The same variants can differentiate the links between ε4 and neuroimaging markers.
Signatures of the Correlated‐Hopping Interaction in Non‐Linear Transport Through a Quantum Dot
Authors: Eckern Ulrich , Wysokiński Karol I. 
Published: December 2024

AbstractIn condensed matter systems with the Coulomb interaction playing an important role one expects, besides the on‐site (local) Hubbard‐type interaction, that also other (non‐local) terms depending on the site occupancy, known as correlated or assisted hopping, exist. Even though such terms in quantum dots tunnel coupled to external electrodes may have quite an appreciable amplitude, the interpretation of experiments on these systems—usually in the linear response regime—seems not to require their presence. However, since the correlated‐hopping term breaks the particle‐hole symmetry of the standard Anderson model and modifies all transport characteristics of the system, the detailed knowledge of its influence on measurable characteristics, especially in the non‐linear regime, is a prerequisite for its experimental detection. In this paper, the non‐linear transport properties of junctions composed of a quantum dot tunnel coupled to external electrodes are studied. The system is modeled by the single‐impurity Anderson Hamiltonian with Hubbard on‐site interaction and with a non‐local correlated‐hopping interaction. Using the previously found general expression for the spin‐dependent transport and spectral Green functions as well as general formulae for charge and heat transport, relevant transport characteristics are calculated in the strongly non‐linear regime.