bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions
Authors: Ye Wenpeng , Meng Zhengong , Zhan Guixiang , Lv Anqi , Gao Yanhua , Shen Kang , Ma Huili , Shi Huifang , Yao Wei , Wang Lin , Huang Wei , An Zhongfu 
Published: November 2024

AbstractOrganic room‐temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade‐off issue between luminescence efficiency (Φ) and dissymmetry factor (glum) is still challenging to be solved. Here, chiroptical ionic crystals (R/S‐DNP) are constructed through ionization‐induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long‐range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high‐density electrostatic interactions, thus enabling the simultaneous realization of excellent single‐molecule RTP emission and efficient chirality transfer. The synchronous enhancement of ΦP and glum is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric‐driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications.
Strong Chiral Response of Chiral Plasmonic Nanoparticles to Photonic Orbital Angular Momentum
Authors: Lim Yae‐Chan , Kim Ryeong Myeong , Han Jeong Hyun , Aharonovich Igor , Nam Ki Tae , Kim Sejeong 
Published: November 2024

AbstractChiral plasmonic nanomaterials have been widely utilized to study light‐matter interactions due to its capability to amplify chiroptic signals. Conventionally, chiro‐optic experiments have demonstrated interactions between circularly polarized light and materials. However, employing light with chiral phase, i.e., optical vortex, can generate a strong chiral response and holds the potential to unveil extensive material information owing to the infinite topological numbers. In this work, an array of 3D chiral nanoparticles is employed to demonstrate large helical dichroism (HD). Chiral gold nanoparticle arrays are illuminated by vortex beams of opposite helicity, which revealed the high HD value of 0.93. The chiral interaction is theoretically investigated, and enantioselective interaction can be explained by multipole analysis. It is determined that the strong HD is attributed to the interaction of higher‐order multipole moments such as electric quadrupole and magnetic quadrupole moments. This study provides deeper insight into understanding of the interaction between optical vortex and chiral plasmonic nanostructures and paves the way for next‐generation chiroptical applications ranging from ultrasensitive chiral spectroscopy to chiral quantum optics.
Synthesis of Tetrahydro‐β‐carbolines via Cascade Sigmatropic Rearrangements
Authors: Oka Daiki , Ohtsuka Tomomi , Takao Ken‐ichi , Ogura Akihiro 
Published: November 2024

AbstractWe have developed a synthesis for tetrahydro‐β‐carbolines involving cascade sigmatropic rearrangements. The substrates were conveniently prepared from parent anilines via a [2,3]‐sigmatropic rearrangement and cyanomethylation. Silver‐mediated decyanation afforded the corresponding iminium cation, which underwent a cascade consisting of an aza‐Cope rearrangement, an aza‐oxa‐Cope rearrangement, an aromatization, and a Pictet‐Spengler reaction, and tetrahydro‐β‐carbolines were obtained as the single product. The reaction involved seven bond scissions and four bond formations and was triggered by a single reagent.
Real‐Time Lactate Detection in A Dynamic Environment Using Micrsensing Needles
Authors: Tang Yuan‐Sin , Huang Ting‐Wei , Yang Tung‐Lin , Cheng Huei‐Ying , Cheng Yu‐Ting , Tsai Hsiao‐En , Lo Yung‐Chieh , Chen Y. S. 
Published: November 2024

AbstractThis study introduces a novel microneedle‐based lactate sensor with SU‐8 micropillar enhancement, designed for real‐time monitoring in dynamic environments. Utilizing inkjet‐printing technology, the sensor demonstrates enhanced sensitivity and a reduced limit of detection (LoD), addressing critical challenges in clinical applications like hemodialysis and patient monitoring in ICU. Design enhancements in the medical steel needle improve stress resistance during insertion, contributing to the sensor's reliability. The experimental findings demonstrate that the microneedle is capable of achieving a high level of linearity at 0.99, with a sensitivity of 3.38 µA mM−1/mm−2–0.5 µA mM−1/mm−2 observed within the range of 0.1–0.5 mM and 1–10 mM, respectively. Meanwhile, the microneedle exhibits a low limit of detection (LoD) of 0.01 mM when tested in phosphate‐buffered saline (PBS) with varying lactate concentrations. Moreover, it demonstrates a linearity of 0.98, sensitivity of 1.13 µA mM−1 mm−2, and the same LoD of 0.01 mM in urine. The sensor maintains its performance at flow rates up to 500 mL min−1. Overall, this flexible and inkjet‐printed lactate sensor represents a significant advancement in real‐time clinical monitoring technology.
Caboxylative Coupling of N‐(Arylmethyl)sulfonimides with Allyltributylstannane Catalyzed by Palladium Nanoparticles Involving Benzylic C−N Cleavage
Authors: Wu Chaolin , Xie Yanlong , Song Jiliang , Feng Xiujuan , Jian Siqi , Lu Wenchao , Zhu Jiuzhen , Yamamoto Yoshinori , Bao Ming 
Published: November 2024

AbstractThe palladium‐catalyzed three‐component coupling of aryl (hetero) methylsulfonamide, allyltributyltin and carbon dioxide (carboxylative Stille coupling reaction) was successfully conduced to produce β,γ‐unsaturated esters in satisfactory to good yields. The reaction was carried out under mild conditions by using in situ generated palladium nanoparticles as catalyst through the formation of π‐allylpalladium sulfonamide intermediates in the presence of tetrabutylammonium bromide (TBAB).
Selective SNH Alkylamination of 3(5,6,7,8)‐Nitroquinoline and 5‐Nitroisoquinoline in an Aqueous Medium
Authors: Larin Alexander N. , Borovleva Anastasia A. , Demidov Oleg P. , Avakyan Elena K. , Zubenko Alexander A. , Pobedinskaya Diana Yu. , Ermolenko Artem P. , Kolosov Stepan E. , Borovlev Ivan V. 
Published: November 2024

AbstractDirect oxidative SNH alkylamination of 3‐, 5‐, 6‐, 7‐, 8‐nitroquinolines and 5‐nitroisoquinoline in an aqueous solution of an aliphatic amines gives rise to the corresponding alkylamino and dialkylamino derivatives of these nitrohetarenes. The nitro group solely dictates the regioselectivity of reactions. The antibacterial activity of some of them has been studied.
Zinc‐Catalysed (3+2) Cycloaddition of Enaminone with Tosylhydrazide to Synthesise 1H‐Pyrazole via C−N and S−N Bond Cleavage
Authors: Roy Sanjukta , Chatterjee Rana , Dandela Rambabu 
Published: November 2024

AbstractA novel and practical zinc‐catalysed synthesis of 1H‐pyrazole has been developed. The one‐pot protocol enables the cycloaddition of enaminone and tosylhydrazide via C−N and S−N bond breaking process, leading to diverse mono‐substituted pyrazole derivatives in high yields. Moreover, the easily accessible materials, broad substrate scope with excellent functional group tolerance, ease of isolation and open‐air conditions are the key features of the present method.
Distinct Constructs Underlie Patient‐Reported and Performance‐Rated Outcomes after Stroke
Authors: DiCarlo Julie A. , Jaywant Abhishek , Gochyyev Perman , Bonkhoff Anna K. , Hardstone Richard , Erler Kimberly S. , Ranford Jessica , Cloutier Alison , Ward Nathan , Sloane Kelly L. , Schwamm Lee H. , Cramer Steven C. , Lin David J. 
Published: November 2024

ObjectivePatient‐reported outcome measures (PROMs), which capture patients' perspectives on the consequences of health and disease, are widely used in neurological care and research. However, it is unclear how PROMs relate to performance‐rated impairments. Sociodemographic factors are known to affect PROMs. Direct damage to brain regions critical for self‐awareness (i.e., parietal regions and the salience/ventral‐attention network) may also impair self‐report outcomes. This study examined the relationship between PROMs and performance‐based measures in stroke survivors with arm motor impairments. We hypothesized that PROMs would be distinct from performance‐based outcomes, influenced by sociodemographic factors, and linked to damage in brain circuits involved in self‐perception.MethodsWe longitudinally assessed 54 stroke survivors using patient‐reported and performance‐rated measures at 4 timepoints. We used factor analysis to reveal the outcome battery's factorial structure. Linear regression examined the association between classes of measures and sociodemographics. Voxel‐lesion‐symptom‐mapping, region‐of‐interest‐based analysis, and voxel‐lesion‐network‐mapping investigated the relationship between classes of outcomes and stroke‐related injury.ResultsPerformance‐based and patient‐reported measures formed distinct factors, consistent across recovery phases. Higher education (β1 = 0.36, p = 0.02) and income adequacy (β2 = 0.48, p = 0.05) were associated with patient‐reported, but not performance‐rated outcomes. Greater parietal lobe injury, irrespective of hemisphere, was associated with worse patient‐reported outcomes; greater corticospinal tract injury related to worse performance‐rated outcomes. Lesions with greater functional connectivity to the salience/ventral‐attention network were associated with worse patient‐reported outcomes (r = −0.35, p = 0.009).InterpretationOur findings reveal important differences between performance‐rated and patient‐reported outcomes, each with specific associated factors and anatomy post‐stroke. Incorporating sociodemographic and neuroanatomic characteristics into neurorehabilitation strategies may inform and optimize patient outcomes. ANN NEUROL 2025;97:242–253
Production of Branched Alkanes by Upcycling of Waste Polyethylene over Controlled Acid Sites of SO4/ZrO2‐Al2O3 Catalyst
Authors: Han Wanying , Lin Longfei , Cen Ziyu , Ke Yubin , Xu Qian , Zhu Junfa , Mei Xuelei , Xia Zhanghui , Zheng Xinrui , Wang Yaqin , Liu Yani , He Mingyuan , Wu Haihong , Han Buxing 
Published: November 2024

AbstractBranched alkanes, which enhance the octane number of gasoline, can be produced from waste polyethylene. However, achieving highly selective production of branched alkanes presents a significant challenge in the upcycling of waste polyethylene. Here, we report a one‐pot process to convert polyethylene into gasoline‐range hydrocarbons (C4–C13) with yield of 73.3 % over SO4/ZrO2‐Al2O3 catalyst at 280 °C. The proportion of branched alkanes reaches 90.1 % within the C4–C13 fraction. Incorporation of sulfate group endows the catalyst with strong Lewis acid sites and weak and moderate Brønsted acid sites. In situ X‐ray absorption, in situ infrared spectroscopy, in situ small angle neutron scattering, and DFT calculations reveal that polyethylene activation occurs through the synergy between sulfate groups and strong Lewis acid sites (Zr sites). The weak and moderate Brønsted acid sites preferentially catalyze the isomerization and type A β‐scission processes, which favors the formation of branched alkanes, while suppressing competing reactions that produce straight‐chain alkanes.
Activating Oxygen via the 3‐Electron Pathway to Hydroxyl Radical by La−O4 Single‐atom on WO3 for Water Purification
Authors: Zhou Zhiruo , Zhao Shiyi , Li Zhihao , Wang Pengfei , Zhan Sihui , Wang Meizhen 
Published: November 2024

AbstractShifting photocatalytic oxygen activation towards 3‐electron (e−) pathway to hydroxyl radicals, instead of the normal 1 e− to superoxide radicals, becomes increasingly important for pollution degradation since hydroxyl radicals possess a high oxidation potential (2.80 V). Here, we demonstrate a selective oxygen activation to hydroxyl radicals via 3 e− pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La−O coordination strength (denoted as LaO4−WOv). Unsaturated‐state La overcomes the rate‐limited step of 2 e− oxygen reduction reaction towards to hydrogen peroxide via tuning binding free energy of key reaction intermediate *OOH, stepped by easy generation of hydroxyl radicals via 1 e−. This strategy alters the activation of oxygen process from 1 e− to 3 e−. Hydrogen peroxide and hydroxyl radicals over LaO4−WOv produces 3.8 and 3.3 mmol L−1 h−1, 35 and 8 times that of detected over WO3, respectively. Rapid and complete removal of tetracycline realizes over LaO4−WOv with 0.077 min−1 of rate constant, 38 times that of WO3. Degradation efficiencies keep greater than 98 % following five repeats, revealing a practical‐utilization‐level robust stability. This work builds an unsaturated‐state transition metal site for manipulating oxygen activation towards an effective water purification as a representative application.
Modulation for Redox States of Single‐Walled Carbon Nanotubes: Effect of Wrapping Conjugated Polymers
Authors: Wu Siyuan , Zhu Haibiao , Hong Liu , Nakashima Naotoshi , Yang Cheng 
Published: November 2024

AbstractControlling the redox states of single‐walled carbon nanotubes (SWNTs) is important for the optimization of their real performances in various fields. By means of in situ photoluminescence (PL) spectroelectrochemical measurements, we report a successful modulation for the redox parameters (redox potentials and electrochemical band gap) of (6,5) and (7,5)SWNTs with a simple change in conjugated polymers (CPs) non‐covalently wrapped on the nanotubes. The large shift in the band gap (187 meV for (6,5)SWNTs and 101 meV for (7,5)SWNTs) was connected to the prominent difference in the interactions between the CPs and SWNTs as suggested by molecular dynamics (MD) simulations, while a striking difference in the π‐electrons states of CP/SWNTs enabled the tuning of SWNTs’ electronic states. Asymmetrical modulation for the reduction potential (LUMO) and oxidation potential (HOMO) of the SWNTs was observed as well. Our results can be promising for a simple but precise control of the electric states of SWNTs.
A Sequential Learning Procedure for Estimating Coefficients in Linear Regression With Applications to Online Sales Examination
Authors: Hu Jun , Zhuang Yan , Zhao Shunan 
Published: November 2024

ABSTRACTIn this paper, we consider the problem of estimating coefficients in a linear regression model. We propose a sequential learning procedure to determine the sample size for achieving a given small estimation risk, under the widely used Gauss‐Markov setup with independent normal errors. The procedure is proven to enjoy the second‐order efficiency and risk‐efficiency properties, which are validated through Monte Carlo simulation studies. Using e‐commerce data, we implement the procedure to examine the influential factors of online sales.
Fructus Arctii Mitigates Depressive Disorder via the Let‐7e‐Modulated Toll‐Like Receptor (TLR) Signaling Pathway
Authors: Zhang Weifang , Zhou Qin 
Published: November 2024

ABSTRACTBackgroundDepressive disorder is a common and serious public health challenge globally. Fructus arctii is a traditional medicinal plant ingredient with diverse pharmacological effects. This study aimed to investigate the therapeutic potential of Fructus arctii in alleviating depressive‐like behaviors.Materials and MethodsWe established a chronic unpredictable mild stress (CUMS)‐induced depression mouse model to assess the antidepressant effects of Fructus arctii. BV2 cells treated with lipopolysaccharide (LPS) were used to mimic neuronal damage. Behavioral tests, including the sucrose preference test, tail‐suspension test, and forced swim test, were conducted to evaluate the impact of Fructus arctii on depressive‐like behaviors. Let‐7e expression was detected by RT‐qPCR, and TLR4 signaling pathway activation was evaluated by western blot analysis, which also assessed the inflammatory response by measuring levels of IL‐6, IL‐1β, MCP‐1, TNF‐α, and iNOS. Immunohistological analysis was conducted to detect the expression of microglia markers. Luciferase reporter assays verified the interaction between let‐7e and TLR4.ResultsFructus arctii administration effectively alleviated depressive‐like behaviors induced by CUMS in mice, as evidenced by improved sucrose preference and reduced immobility time in behavioral tests. Mechanistically, Fructus arctii reversed the CUMS‐induced downregulation of let‐7e and upregulation of TLR4 and MyD88 protein levels in mice hippocampus tissues. In addition, Fructus arctii suppressed microglial activation and reduced the levels of inflammatory factors by upregulating let‐7e. Let‐7e was verified to bind to TLR4, thereby negatively regulating its expression. TLR4 overexpression reversed the suppressive effect of let‐7e upregulation on inflammatory reactions and microglial activation. Furthermore, intracerebroventricular injection of let‐7e agomiR alleviated depressive‐like behavior and inhibited microglial activation in vivo.ConclusionIn summary, Fructus arctii mitigates depression by regulating the let‐7e/TLR4/MyD88 pathway, offering new insights into potential depression therapies.
Towards Bacterial Resistance via the Membrane Strategy: Enzymatic, Biophysical and Biomimetic Studies of the Lipid cis‐trans Isomerase of Pseudomonas aeruginosa
Authors: Mauger Mickaël , Makarchuk Iryna , Molter Yasmin , Sansone Anna , Melin Frédéric , Chaignon Philippe , Schaeffer Philippe , Adam Pierre , Schünemann Volker , Hellwig Petra , Ferreri Carla , Chatgilialoglu Chryssostomos , Seemann Myriam 
Published: November 2024

AbstractThe lipid cis‐trans isomerase (Cti) is a periplasmic heme‐c enzyme found in several bacteria including Pseudomonas aeruginosa, a pathogen known for causing nosocomial infections. This metalloenzyme catalyzes the cis‐trans isomerization of unsaturated fatty acids in order to rapidly modulate membrane fluidity in response to stresses that impede bacterial growth. As a consequence, breakthrough in the elucidation of the mechanism of this metalloenzyme might lead to new strategies to combat bacterial antibiotic resistance. We report the first comprehensive biochemical, electrochemical and spectroscopic characterization of a Cti enzyme. This has been possible by the successful purification of Cti from P. aeruginosa (Pa‐Cti) in favorable yields with enzyme activity of 0.41 μmol/min/mg when tested with palmitoleic acid. Through a synergistic approach involving enzymology, site‐directed mutagenesis, Raman spectroscopy, Mössbauer spectroscopy and electrochemistry, we identified the heme coordination and redox state, pinpointing Met163 as the sixth ligand of the FeII of heme‐c in Pa‐Cti. Significantly, the development of an innovative assay based on liposomes demonstrated for the first time that Cti catalyzes cis‐trans isomerization directly using phospholipids as substrates without the need of protein partners, answering the important question about the substrate of Cti within the bacterial membrane.
Investigating the Prevalence of Hypercalciuria in Children Aged 2–16 Years With Asymptomatic Microscopic Hematuria in 2020 in Tehran Children's Medical Center
Authors: MohammadKhawajah Izat , Shamshiri Khamene Sima , Mahboobipour Amir Ali , Radmehr Elahe , Moghtaderi Mastaneh 
Published: November 2024

ABSTRACTThe prevalence of hypercalciuria in children is 3%–10% globally and up to 35% in the United States. Hypercalciuria in children has many presentations; it causes different metabolic disorders and can negatively affect a child's growth. It also increases the risk of low bone mineral density and urinary tract infections. In addition, it is the most widespread cause of persistent microscopic hematuria. Changes in the diet and medications in cases of advanced stage can be useful to prevent further complications. This study aimed to determine the prevalence of hypercalciuria and to investigate its relationship with different factors in children aged 2–16 years with asymptomatic microscopic hematuria in 2020 in the Children's Medical Center hospital. This retrospective cross‐sectional study was performed in a population of children aged 2–16 years old with asymptomatic microscopic hematuria who were referred to the Children's Medical Center clinic in 2020. Data such as age, sex, serum creatinine level, and proteinuria were extracted from the patient's medical records, and their relationship with hypercalciuria was analyzed using logistic regression analysis. According to the inclusion criteria, 166 children with asymptomatic microscopic hematuria (72 boys and 94 girls) were included in this study. The prevalence of hypercalciuria (ratio of random urine calcium to creatinine more than 0.2) in these patients was estimated at 25% with a confidence interval of 18%–32%. In order of prevalence, the most common conditions accompanying microscopic hematuria were kidney stones, urinary tract infections, and proteinuria. The age of patients with hypercalciuria was 2 years younger on average. Each year of age increase and every 5 years of age increase between the ages of 2 and 16 years reduced the chance of hypercalciuria in this category of patients by 12% and 45%, respectively. Our findings also showed that children with a positive history of kidney stones were about 2.2 times more likely to have hypercalciuria than their counterparts, which is considered a medium effect size. Our results showed that hypercalciuria in children with hematuria is significantly related to younger age and a positive history of kidney stones.
Functionalization of Emulsion Interfaces: Surface Chemistry Made Liquid
Authors: Courrégelongue Clémence , Baigl Damien 
Published: November 2024

AbstractDisperse systems, and emulsions in particular, are currently massively used in fields as varied as food industry, cosmetics, health care and environmentally‐friendly materials. To meet increasingly precise needs or targeted applications, these systems need to be endowed with new functionalities at their interfaces, in addition to their composition and structural properties. However, due to the fragility of drops and the low reactivity of their surface, conventional solid surface chemistry cannot be used for such a purpose. Several specific emulsion interface functionalization techniques have thus been developed for targeted systems and applications, but a general framework has yet to be drawn. In this review, we attempt to present these methods in a unified way through the prism of what we may call “liquid surface chemistry”. We propose to categorize existing methods into drop‐coating strategies, including layer‐by‐layer techniques and polymer coating, with a particular focus on polydopamine, and emulsifier‐carrier approaches involving particles and/or amphiphilic molecules. They are discussed in a transversal way, highlighting the underlying physico‐chemical principles and providing a comparative analysis of their advantages, current limitations and potential for improvement. We also propose future directions and opportunities, involving for instance DNA‐based programmability or artificial intelligence, which could make liquid surface chemistry more versatile and controlled.