bluuebunny/crossref_metadata_2025_split huggingface dataset:
Neighborhood Disadvantage and Knee Osteoarthritis Pain: Do Sleep and Catastrophizing Play a Role?
Authors: Huber Felicitas A. , Gonzalez Cesar , Kusko Daniel A. , Mickle Angela , Sibille Kimberly T. , Redden David T. , Azuero Casey B. , Staud Roland , Fillingim Roger B. , Goodin Burel R. 
Published: October 2024

ObjectiveThe objective was to examine potential pathways linking neighborhood disadvantage to pain severity in individuals with knee pain consistent with or at risk for knee osteoarthritis (KOA).MethodsThe current investigation is a cross‐sectional analysis. Data were collected from 140 middle‐aged to older non‐Hispanic White and non‐Hispanic Black adults from the Understanding Pain and Limitations in Osteoarthritic Disease Study 2 (UPLOAD‐2). Relationships among neighborhood disadvantage, sleep efficiency, pain catastrophizing, and pain severity were assessed. Neighborhood disadvantage was quantified using the Area Deprivation Index, and actigraphy data were used to assess sleep efficiency. The Coping Strategies Questionnaire–Revised catastrophizing subscale and the Western Ontario and McMaster Universities Osteoarthritis Index pain severity scale were used to assess pain catastrophizing and pain severity, respectively. A serial mediation model assessed the neighborhood–sleep–catastrophizing–pain pathway, as well as the neighborhood–sleep–pain and the neighborhood–catastrophizing–pain pathways.ResultsGreater neighborhood disadvantage was associated with worse sleep efficiency, ultimately contributing to greater pain severity. Although neither neighborhood disadvantage nor sleep efficiency were associated with pain catastrophizing, pain catastrophizing itself was associated with greater KOA pain.ConclusionNeighborhood disadvantage impacts KOA pain outcomes through sleep efficiency but not pain catastrophizing, thereby highlighting environmental aspects that impact sleep as potential targets for intervention.
Lyotropic Liquid Crystalline Based Nasal Spray for Improved Parkinson's Treatment: Enhanced Superior Nasal Tract Deposition and Antioxidation Strategy
Authors: Xia Xiao , Zhong Ziqiao , Wei Chunfu , Wang Guanlin , Zhao Ziyu , He Jingyu , Zhai Zizhao , Zhou Yue , Wang Wenhao , Guo Haihua , Jin Yuzhen , Liu Cenfeng , Yue Xiao , Wu Chuanbin , Huang Ying , Zhang Xuejuan 
Published: October 2024

AbstractThe blood–brain barrier is one of the serious challenges in the treatment of Parkinson's disease (PD), which severely hinders the drug's brain bioavailability. In this study, a lyotropic liquid crystalline (LLC) based in situ gel nasal spray loaded with the first‐line drug Levodopa (LDA) for PD is developed to resolve this issue based on a nose‐to‐brain drug delivery approach. Specifically, the two key stages of LLC‐based in situ gel nasal spray, droplet deposition, and drug retention are tailored. By adjusting LLC's precursor solution's viscosity, the droplet deposition on the superior nasal tract can be increased by 18 times. Through nasal mucus‐triggered sol–gel transition, the LDA nasal cavity retention is prolonged by three times. The epigallocatechin gallate is incorporated into the LLC‐based in situ gel nasal spray to inhibit the autoxidation of LDA and alleviate the oxidative stress response in PD. The results show that the LLC‐based in situ gel nasal spray has a 26‐fold higher brain bioavailability of LDA compared to oral administration. The PD rats show a significant improvement in behavioral and cognitive disorders after administration. The LLC‐based in situ gel nasal spray is proved to work by reducing oxidative damage. This study is anticipated to offer a promising strategy for the clinical application of LDA.
All‐Climate Thermal Management Performance of Power Batteries Based on Double‐Layer Flexible Phase Change Materials
Authors: Liu Meng , Li Xulong , Qian Runda , Lu Xitao , Liu Yifan , Zou Deqiu 
Published: October 2024

AbstractThermal management systems for power batteries based on phase change materials (PCM) are limited by low heat transfer efficiency, leakage issues, and high rigidity, and most of them cannot meet the needs of all‐climate thermal management. A double‐layer flexible phase change material (FPCM) sleeve structure for all‐climate thermal management is proposed in this study for the first time. Innovations in both material and design have enhanced the adaptability of the thermal management system. The outer layer FPCM achieves high thermal conductivity (4.23 W m−1 K−1) and electrical conductivity (0.95 S m−1), the inner layer FPCM achieves insulation (22.76 MΩ) and flexibility, the thermal contact resistance (TCR) between the double‐layer sleeve structure and the battery are measured to be only 0.15 °C W−1, significantly improved thermal management performance. Experimental results show that at 30 °C ambient temperature, 5 C discharge, the system reduces the maximum temperature by 14.5 °C, from 61.4 to 46.9 °C, compared to natural convection. Additionally, during heating, the system achieves heating rates of 7.0, 8.3, and 8.7 °C min−1 at −20, −10, and 0 °C, respectively, extending battery discharge duration by 32.5%, 65.9%, and 33.6%.
Voxel Interface Control in Multimaterial Extrusion 3D Printing
Authors: Ames Daniel C. , Propst Sarah , Shah Aadarsh , Mueller Jochen 
Published: October 2024

AbstractInterfaces are crucial in natural and engineered systems, dictating essential biological, ecological, and technological properties that augment performance, functionality, and user experience. Yet, achieving precise interfacial control poses significant challenges in both conventional and additive manufacturing, where scalability constraints impede the controlled deposition of quasi‐2D layers within 3D objects. This paper introduces Voxel‐Interface 3D Printing (VI3DP), which enables comprehensive control over extruded voxel interfaces irrespective of the printhead diameter that conventionally dictates feature size. Various optical, mechanical, and electrical functionalizations, attaining interface thicknesses up to three orders of magnitude smaller than the voxel size are reported. Notable applications include encoding data in soft matter through fluorescent interfaces, creating tight fits and movable mechanisms through non‐adhesive interfaces, fabricating bio‐inspired composites with tailored failure modes, and developing a single filament capacitive touch sensor. VI3DP opens new avenues for enhanced functionality and efficiency across multiple fields, including biomedical technology, electronics, optics, and nanotechnology.
Ultrahigh Energy Storage of Twisted Structures in Supramolecular Polymers
Authors: Li Jinfeng , Gao Yan , Jin Yupeng , Zhang Tian 
Published: October 2024

AbstractPolymer dielectrics possess outstanding advantages for high‐power energy storage applications such as high breakdown strength (Eb) and efficiency (η), while both of them decrease rapidly at elevated temperatures. Although several strategies have been evaluated to enhance Eb and heat resistance, the discharged energy density (Ud) is still limited by the planar conjugated structure. In this study, a novel approach to manipulate polymer morphology is introduced, thereby influencing dielectric properties. A range of polyurea (PU)‐based polymers are predicted from different structural unit combinations by machine learning and synthesized two representative polymers with high dielectric constants (K) and thermal stability. These polymers are combined with PI to form a twisted polymer via hydrogen bonding interactions (HNP). Both experimental results and computational simulations demonstrate the twisted structure disrupts the conjugated structure to widen the bandgap and increase dipole moment through the twisting of polar groups, leading to simultaneous improvements in both K and Eb. Consequently, HNP‐20% achieves an ultrahigh Ud of 6.42 J cm−3 with an efficiency exceeding 90% at 200 °C. This work opens a new avenue to scalable high Ud all‐polymer dielectric for high‐temperature applications.
Nickel‐Doped Facet‐Selective Copper Nanowires for Activating CO‐to‐Ethanol Electrosynthesis
Authors: Zhang Xing , Ling Chongyi , Ren Siyun , Xi Hanchen , Ji Liyao , Wang Jinlan , Zhu Jia 
Published: October 2024

AbstractEthanol isa promising energy vector for closing the anthropogenic carbon cycle through reversible electrochemical redox. Currently, ethanol electrosynthesissuffers from low product selectivity due to the competitive advantage of ethylene in CO2/CO electroreduction. Here, a facet‐selective metal‐doping strategy is reported, tuning the reaction kinetics of CO reduction paths and thus enhancing the ethanol selectivity. The theoretical calculations reveal that nickel (Ni)doped Cu(100) surface facilitates water dissociation to form adsorbed hydrogen, which promotesselective electrochemical hydrogenation of a key C2 intermediate (*CHCOH) toward ethanol path over ethylene path. Experimentally, a solution‐phase synthesis of a Ni‐doped {100}‐dominated Copper nanowires (Cu NWs) catalyst is reported, enabling an ethanol Faradaic efficiency of 56% and a selectivity ratio of ethanol to ethylene of 2.7, which are ≈4 and 15 times larger than those of undoped Cu NWs, respectively. The operando spectroscopic characterizations confirm that Ni‐doping in Cu NWs can alter the interfacial water activity and thus regulate the C2 product selectivity. With further electrode engineering, a membrane electrode assembly electrolyzer using Ni‐doped Cu NWs catalysts demonstrates an ethanol Faradaic efficiency over 50% at 300 mA cm−2 with a full cell voltage of ≈2.7 V and operates stably for over 300 h.
Exploring the Frontiers of Cell Temperature Measurement and Thermogenesis
Authors: Zhu Hanliang , Xu Haotian , Zhang Yue , Brodský Jan , Gablech Imrich , Korabečná Marie , Neuzil Pavel 
Published: October 2024

AbstractThe precise measurement of cell temperature and an in‐depth understanding of thermogenic processes are critical in unraveling the complexities of cellular metabolism and its implications for health and disease. This review focuses on the mechanisms of local temperature generation within cells and the array of methods developed for accurate temperature assessment. The contact and noncontact techniques are introduced, including infrared thermography, fluorescence thermometry, and other innovative approaches to localized temperature measurement. The role of thermogenesis in cellular metabolism, highlighting the integral function of temperature regulation in cellular processes, environmental adaptation, and the implications of thermogenic dysregulation in diseases such as metabolic disorders and cancer are further discussed. The challenges and limitations in this field are critically analyzed while technological advancements and future directions are proposed to overcome these barriers. This review aims to provide a consolidated resource for current methodologies, stimulate discussion on the limitations and challenges, and inspire future innovations in the study of cellular thermodynamics.
Metal–Organic Framework and Covalent–Organic Framework‐Based Aerogels: Synthesis, Functionality, and Applications
Authors: Shao Gaofeng , Huang Xiaogu , Shen Xiaodong , Li Changxia , Thomas Arne 
Published: October 2024

AbstractMetal–organic frameworks (MOFs) and covalent–organic frameworks (COFs)‐based aerogels are garnering significant attention owing to their unique chemical and structural properties. These materials harmoniously combine the advantages of MOFs and COFs—such as high surface area, customizable porosity, and varied chemical functionality—with the lightweight and structured porosity characteristic of aerogels. This combination opens up new avenues for advanced applications in fields where material efficiency and enhanced functionality are critical. This review provides a comparative overview of the synthetic strategies utilized to produce pristine MOF/COF aerogels as well as MOF/COF‐based hybrid aerogels, which are functionalized with molecular precursors and nanoscale materials. The versatility of these aerogels positions them as promising candidates for addressing complex challenges in environmental remediation, energy storage and conversion, sustainable water‐energy technologies, and chemical separations. Furthermore, this study discusses the current challenges and future prospects related to the synthesis techniques and applications of MOF/COF aerogels.
Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes
Authors: Zi Quan‐Xing , Shu Wei 
Published: October 2024

AbstractEnantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni‐catalyzed reductive‐oxidative relay cross‐coupling of two alkenes is developed for the first time. The reaction features the use of enol esters and unactivated alkenes as two different alkyl equivalents to undergo head‐to‐tail and enantioselective alkyl‐alkyl cross‐coupling. The reaction undergoes two‐electron reduction and single electron oxidation in the presence of both reductants and oxidants. The use of an allyl bromide as single electron acceptor is crucial for the success of this non‐trivial asymmetric cross‐coupling, providing a new reaction mode for asymmetric alkyl‐alkyl bond‐forming event in the absence of stoichiometric alkyl electrophiles.
Developing Practical Catalysts for High‐Current‐Density Water Electrolysis
Authors: Zhang Xiaohan , Cao Chentian , Ling Tao , Ye Chao , Lu Jian , Shan Jieqiong 
Published: October 2024

AbstractHigh‐current‐density water electrolysis is considered a promising technology for industrial‐scale green hydrogen production, which is of significant value to energy decarbonization and numerous sustainable industrial applications. To date, substantial research advancements are achieved in catalyst design for laboratory‐based water electrolysis. While the designed catalysts demonstrate remarkable performance at laboratory‐based low current densities, they suffer from marked deteriorations in both activity and long‐term stability under industrial‐level high‐current‐density operations. To provide a timely assessment that helps bridge the gap between laboratory‐scale fundamental research and industrial‐scale practical water electrolysis technology, here the current advancements in various commercial water electrolyzers are first systematically analyzed, then the key parameters including work temperature, current density, lifetime of stacks, cell efficiency, and capital cost of stacks are critically evaluated. In addition, the impact of high current density on the electrocatalytic behavior of catalysts, including intrinsic activity, long‐term stability, and mass transfer, is discussed to advance the catalyst design. Therefore, by covering a range of critical issues from fundamental material design principles to industrial‐scale performance parameters, here the future research directions in the development of highly efficient and low‐cost catalysts are presented and a procedure for screening laboratory‐designed catalysts for industrial‐scale water electrolysis is outlined.
Population History and Anthropometric Variation of West Coast Irish Islands
Authors: Relethford John H. 
Published: October 2024

ABSTRACTObjectivesPrevious research using anthropometric data from the west coast of Ireland in the late 19th century showed that two island populations, the Aran Islands and Inishbofin, were phenotypically divergent from the mainland and more similar to England, a pattern consistent with historical evidence for English admixture. The present study extends these analyses by including data from two other island populations in the region that do not have a history of English admixture.Materials and MethodsData were taken from published sources for six west coast Irish populations measured in the 1890s: two mainland groups (Connemara and Erris) and four island populations (the Aran Islands, Clare Island, Inishbofin, and the Inishkea Islands). The anthropometric data consist of 13 measures on 317 males. Mahalanobis distances among the six populations were derived as well as distances to a mean based on English anthropometric data.ResultsThe two island populations with a history of likely English admixture following the garrisoning of English soldiers in previous centuries were the most divergent from the Irish mainland and most similar to the English mean. The other two island populations (Clare Island and the Inishkea Islands) did not have a history of English admixture and were most similar to the Irish mainland.DiscussionThe different patterns of anthropometric similarity among the four island populations show different population histories and support earlier studies suggesting differential English admixture as a factor in the population structure of the region.
A Facile and Regioselective Synthesis of 2‐Formamidothiazoles via the C−H Formamidation of Thiazole N‐Oxides with Isocyanides
Authors: Zhang Yanqiu , Lu Qianchen , Wang Jiayi , Song Gonghua 
Published: October 2024

AbstractA facile, microwave‐promoted, regioselective C−H formamidation of thiazole N‐oxides with isocyanides in the presence of TBDPSCl was developed. Various 2‐(N‐substituted formamido)thiazoles were obtained in moderate to high yields. In the case of the C2‐substituted thiazole N‐oxides, the C−H formamidation took place selectively at the C4 position of the thiazole ring. This transformation is also applicable to some other N‐containing heterocyclic derivatives such as pyridine, quinoline, and pyridazine N‐oxides and has advantages such as broad substrate tolerance, high regioselectivity, and mild reaction conditions.
Development of the Esterase PestE for Amide Bond Synthesis Under Aqueous Conditions: Enzyme Cascades for Converting Waste PET into Tamibarotene
Authors: Goulding Ellie , Ward Lucy C. , Allan Faye E. , Dittman Drew , Salcedo‐Sora Jesus E. , Carnell Andrew J. 
Published: October 2024

AbstractA growing number of hydrolase enzymes show promiscuous acyltransferase activity, even under aqueous conditions. Here we report, for the first time, the ability of Pyrobaculum calidifontis VA1 esterase (PestE) to catalyse the formation of a wide range of amides in buffer, where the acyl donor forms a significant structural component in the amide product. The reactions occur under mild conditions and can achieve conversions up to 97 % in 6 h for formation of N‐benzylfuranamide as the model reaction. We demonstrate PestE's potential in enzyme cascades to make amides from waste PET plastic and the conversion of the terephthalic acid product to tamibarotene, a drug with activity against acute leukemia. Rational mutagenesis led to identification of PestE variants F33L F289A and F33L. F33L F289A increased conversion of N‐benzylfuranamide by 1.2‐fold, and F33L gave a 4‐fold increase in conversion to tamibarotene.
Stereochemical Impacts on Acyclic Mechanochemical Carbon‐Carbon Bond Activation
Authors: Schwarz Rony , Manor Armon Amit , Diesendruck Charles E. 
Published: October 2024

AbstractThe influence of stereochemistry on the mechanochemistry rate is studied using a new mechanophore based on a benzopinacol (BP) skeleton. Two sets of BP diastereomers, the meso R,S and the R,R/S,S were isolated, incorporated into the center of a poly(methyl acrylate), and their mechanical activation rate was measured in solution. Under mechanical stress, the central C−C bond in BP is cleaved, providing two independent benzophenone molecules with higher UV‐absorption coefficient at 254 nm. Monitoring the reaction rate spectroscopically indicates that the chiral R,R/S,S enantiomers react ~1.4 fold faster compared to the meso R,S diastereomer. In‐silico modeling indicates that a hydrogen bond between the syn hydroxyls in the R,R diastereomer becomes shorter with stress, reducing the maximal force required for C−C bond scission, while this bond is inexistent in the meso diastereomer, as the hydroxyl are anti to each other. Our results indicate that in polymer where free rotation around bonds is possible, non‐covalent interactions between backbone substituents, which are affected by relative stereochemistry, can play a fundamental role in the mechanochemical stability of the polymer.
A 3D Robust and Microporous B←N Framework with 8‐connected Sandwich Nodes for Efficient Separation of Hexane Isomers
Authors: Lin Hongyu , Zhang Hao , Li Yunbin , Yuan Furong , Zheng Xiaoqing , He Lei , Li Lu , Zhang Yongfan , Xiang Shengchang , Chen Banglin , Zhang Zhangjing 
Published: October 2024

AbstractRecently B←N organic frameworks (BNFs) have gained substantial attention owing to their unique dative bond energy, which imparts them with specialized functionalities across a broad spectrum of applications. Despite previous reports on BNFs with permanent porosity, research endeavors towards three‐dimensional (3D) BNFs with similar properties are scarce, with no report of robust 3D BNFs featuring permanent porosity to date. Herein, electrostatic complementary strategy is proposed to construct the first example of 3D robust and microporous BNF, BNF‐100, featuring a reo topology with 8‐connected sandwich nodes assembled via dative B←N bonds. The activated form BNF‐100 a exhibits excellent chemical stability and permanent porosity with Langmuir surface area of 645.9 m2 g−1 and pore volume of 0.23 cm3 g−1. BNF‐100 a can efficiently separate hexane isomers through sieving mechanisms, as confirmed by vapor adsorption experiments and dynamic breakthrough tests, surpassing the performance of most MOF materials. Finally, we achieved the purification of different branched hexane isomers using a single breakthrough column in a combined breakthrough and purging experiment, which is the first reported instance in the literature on hexane isomer separation.
Regulation of Exciton Effects in Functionalized Conjugated Polymers by B‐N Lewis Pairs for Visible‐Light Photocatalysis
Authors: Ru Chenglong , Nie Xiaoyu , Lan Zhi‐An , Pan Zhiming , Xing Wandong , Wang Sibo , Yu Jimmy C. , Hou Yidong , Wang Xinchen 
Published: October 2024

AbstractStrong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far‐reaching in facilitating photocatalysis. A series of B−N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B−N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free‐charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.