bluuebunny/crossref_metadata_2025 huggingface dataset:
Cross‐Linker Architectures Impact Viscoelasticity in Dynamic Covalent Hydrogels
Authors: Lin Yung‐Hao , Lou Junzhe , Xia Yan , Chaudhuri Ovijit
Published: October 2024

Dynamic covalent cross‐linked (DCC) hydrogels represent a significant advance in biomaterials for regenerative medicine and mechanobiology, offering viscoelasticity, and self‐healing properties that more closely mimic in vivo tissue mechanics than traditional, predominantly elastic, covalent hydrogels. However, the effects of varying cross‐linker architecture on DCC hydrogel viscoelasticity have not been thoroughly investigated. This study introduces hydrazone‐based alginate hydrogels to explore how cross‐linker architectures impact stiffness and viscoelasticity. In hydrogels with side‐chain cross‐linker (SCX), higher cross‐linker concentrations enhance stiffness and decelerate stress relaxation, while an off‐stoichiometric hydrazine‐to‐aldehyde ratio reduces stiffness and shortens relaxation time. In hydrogels with telechelic cross‐linking, maximal stiffness and relaxation time occurs at intermediate cross‐linker mixing ratio for both linear cross‐linker (LX) and star cross‐linker (SX), with higher cross‐linker valency further enhancing these properties. Further, the ranges of stiffness and viscoelasticity accessible with the different cross‐linker architectures are found to be distinct, with SCX hydrogels leading to slower stress relaxation relative to the other architectures, and SX hydrogels providing increased stiffness and slower stress relaxation versus LX hydrogels. This research underscores the pivotal role of cross‐linker architecture in defining hydrogel stiffness and viscoelasticity, providing insights for designing DCC hydrogels with tailored mechanical properties for specific biomedical applications.
Boosting Light−Matter Interactions in Plasmonic Nanogaps
Authors: Li Yang , Chen Wen , He Xiaobo , Shi Junjun , Cui Ximin , Sun Jiawei , Xu Hongxing
Published: October 2024

Plasmonic nanogaps in strongly coupled metal nanostructures can confine light to nanoscale regions, leading to huge electric field enhancement. This unique capability makes plasmonic nanogaps powerful platforms for boosting light–matter interactions, thereby enabling the rapid development of novel phenomena and applications. This review traces the progress of nanogap systems characterized by well‐defined morphologies, controllable optical responses, and a focus on achieving extreme performance. The properties of plasmonic gap modes in far‐field resonance and near‐field enhancement are explored and a detailed comparative analysis of nanogap fabrication techniques down to sub‐nanometer scales is provided, including bottom‐up, top‐down, and their combined approaches. Additionally, recent advancements and applications across various frontier research areas are highlighted, including surface‐enhanced spectroscopy, plasmon‐exciton strong coupling, nonlinear optics, optoelectronic devices, and other applications beyond photonics. Finally, the challenges and promising emerging directions in the field are discussed, such as light‐driven atomic effects, molecular optomechanics, and alternative new materials.
Ultrabroadband and >93% Microwave Absorption Enabled by “Doped” Water Meta‐Atom Lattice with Subwavelength Thickness
Authors: Qin Jin , Shi Yuzhi , Jiang Shibin , Gao Yusong , Yao Shupei , Wang Zhanshan , Cheng Xinbin , Tsai Din Ping , Zhang Wu , Zhu Weiming
Published: October 2024

Perfect microwave absorbers, which absorb electromagnetic waves completely, play pivotal roles in electromagnetic shielding, and stealth technologies. Existing microwave absorber technologies rely on either electromagnetic properties of absorptive materials, the resonance behavior of meta‐atoms, or a combination of both. So far, achieving simultaneous broadband absorption, high efficiency, and compact sizes remains a great challenge. Inspired by atomic doping techniques employed in conventional optical materials to broaden spectral bandwidths, a single‐layer microfluidic metasurface microwave absorber is proposed with the assembly of two distinct types of water meta‐atoms. By manipulating electromagnetic resonances of these water meta‐atoms, the metasurface maintains impedance matching over a broad working range. A microwave absorber design with a thickness equivalent to 0.2 times the central wavelength is showcased, measuring over 93% absorption across both K and Ka bands (17.5−40.0 GHz). The results highlight unprecedented superiorities of microwave absorbers based on a 2D doped water meta‐atom lattice when compared to previously reported metasurface absorbers utilizing identical meta‐atoms. This absorber has advantages including small thickness, broad bandwidth, and cost‐effectiveness, making it promising for applications in electromagnetic shielding, camouflage, and multi‐spectral stealth.
Intense and Stable Blue Light Emission From CsPbBr3/Cs4PbBr6 Heterostructures Embedded in Transparent Nanoporous Films
Authors: Romero‐Pérez Carlos , Delgado Natalia Fernández , Collado Miriam Herrera , Calvo Mauricio E. , Míguez Hernán
Published: October 2024

Lead halide perovskite nanocrystals are attractive for light emitting devices both as electroluminescent and color‐converting materials since they combine intense and narrow emissions with good charge injection and transport properties. However, while most perovskite nanocrystals shine at green and red wavelengths, the observation of intense and stable blue emission still remains a challenging target. In this work, a method is reported to attain intense and enduring blue emission (470–480 nm), with a photoluminescence quantum yield (PLQY) of 40%, originating from very small CsPbBr3 nanocrystals (diameter < 3 nm) formed by controllably exposing Cs4PbBr6 to humidity. This process is mediated by the void network of a mesoporous transparent scaffold in which the zero‐dimensional Cs4PbBr6 lattice is embedded, which allows the fine control over water adsorption and condensation that determines the optimization of the synthetic procedure and, eventually, the nanocrystal size. The approach provides a means to attain highly efficient transparent and stable blue light‐emitting films that complete the palette offered by perovskite nanocrystals for lighting and display applications.
Palladium‐Catalyzed Decarboxylative Benzylation and Allylation of Six‐Membered Endocyclic Enecarbamates
Authors: Ruan Junhao , Cao Xi , Zhou Yipeng , Yang Xiaoyu , Chen Weijie
Published: October 2024

Six‐membered endocyclic benzyl/allyl enecarbamates undergo a Pd‐catalyzed decarboxylation process to generate endocyclic 1‐azaallyl anions and Pd–benzyl/allyl cations. The ion pair then react with each other followed by reduction to ultimately give unprotected 2‐(hetero)aryl‐3‐benzylpiperidines and 2‐(hetero)aryl‐3‐allylpiperidines in 31–91% yields as single cis‐diastereomers. These reactions represent a strategy to form unprotected β‐substituted piperidines, which generates elusive endocyclic 1‐azaallyl anion intermediates by introducing the negative charge from the N‐terminal.
Unveiling Metabolic Engineering Strategies by Quantitative Heterologous Pathway Design
Authors: Wei Fan , Cai Jingyi , Mao Yufeng , Wang Ruoyu , Li Haoran , Mao Zhitao , Liao Xiaoping , Li Aonan , Deng Xiaogui , Li Feiran , Yuan Qianqian , Ma Hongwu
Published: October 2024

Constructing efficient cell factories requires the rational design of metabolic pathways, yet quantitatively predicting the potential pathway for breaking stoichiometric yield limit in hosts remains challenging. This leaves it uncertain whether the pathway yield of various products can be enhanced to surpass the stoichiometric yield limit and whether common strategies exist. Here, a high‐quality cross‐species metabolic network model (CSMN) and a quantitative heterologous pathway design algorithm (QHEPath) are developed to address this challenge. Through systematic calculations using CSMN and QHEPath, 12,000 biosynthetic scenarios are evaluated across 300 products and 4 substrates in 5 industrial organisms, revealing that over 70% of product pathway yields can be improved by introducing appropriate heterologous reactions. Thirteen engineering strategies, categorized as carbon‐conserving and energy‐conserving, are identified, with 5 strategies effective for over 100 products. A user‐friendly web server is developed to quantitatively calculate and visualize the product yields and pathways, which successfully predicts biologically plausible strategies validated in literature for multiple products.
Molecular Engineering of a Tumor‐Targeting Thione‐Derived Diketopyrrolopyrrole Photosensitizer to Attain NIR Excitation Over 850 nm for Efficient Dual Phototherapy
Authors: Xu Gang , Song Yunxia , Jin Haifeng , Shi Pengmin , Jiao Yubo , Cao Fangzhou , Pang Jie , Sun Yanyan , Fang Lei , Xia Xing‐Hua , Zhao Jian
Published: October 2024

Photosensitizers with near‐infrared (NIR) excitation, especially above 800 nm which is highly desired for phototherapy, remain rare due to the fast nonradiative relaxation process induced by exciton‐vibration coupling. Here, a diketopyrrolopyrrole‐derived photosensitizer (DTPA‐S) is developed via thionation of carbonyl groups within the diketopyrrolopyrrole skeleton, which results in a large bathochromic shift of 81 nm, endowing the photosensitizer with strong NIR absorption at 712 nm. DTPA‐S is then introduced with a functional biomolecule (N3‐PEG2000‐RGD) via click reaction for the construction of integrin αvβ3 receptor‐targeted nano‐micelles (NanoDTPA‐S/RGD), which endows the photosensitizer with a further superlarge absorption redshift of 138 nm, thus extending the absorption maxima to ≈850 nm. Remarkably, thiocarbonyl substitution increases the nonbonding characters in frontier molecular orbitals, which can effectively suppress the nonradiative vibrational relaxation process via reducing the reorganization energy, enabling efficient reactive oxygen species (ROS) generation under 880 nm excitation. Screened by in vitro and in vivo assays, NanoDTPA‐S/RGD with high water solubility, excellent tumor‐targeting ability, and photodynamic/photothermal therapy synergistic effect exhibits satisfactory phototherapeutic performance. Overall, this study demonstrates a new design of efficient NIR‐triggered diketopyrrolopyrrole photosensitizer with facile installation of functional biomolecules for potential clinical applications.
Non‐volatile and Secure Optical Storage Medium with Multilevel Information Encryption
Authors: Shao Jie , Li Xiyang , Liu Meng , Sun Haiqin , Peng Dengfeng , Liu Fuchi , Zhang Qiwei
Published: October 2024

Non‐volatile photomemory based on photomodulated luminescent materials offers unique advantages over voltage‐driven memory, including low residual crosstalk and high storage speed. However, conventional materials have thus far been volatile and insecure for data storage because of low trap depth and single‐level storage channels. Therefore, the development of a novel non‐volatile multilevel storage medium for data encryption remains a challenge. Herein, a robust, non‐volatile, multilevel optical storage medium is reported, based on a photomodulated Ba3MgSi2O8:Eu3+, which combined the merits of light‐induced valence (Eu3+ → Eu2+) and photochromic phenomena using optical stimulation effects, accompanied by larger luminescent and color contrasts (>90%). These two unique features provided dual‐level storage channels in a single host, significantly improving the data storage security. Notably, dual‐level optical signals could be written and erased simultaneously by alternating 265 and 365 nm light stimuli. Theoretical calculations indicated that robust color centers induced by intrinsic interstitial Mg and vacancy defects with suitable trap depths enable excellent reversibility and long‐term storage capability. By relying on different luminescent readout mechanisms, the encrypted dual‐level information can be accurately decrypted by separately probing the Eu2+ and Eu3+ signals, thus ensuring information security. This study proposes a novel approach for constructing multilevel information storage channels for information security.
An Ultrasensitive and Broad‐Spectrum MoS2 Photodetector with Extrinsic Response Using Surrounding Homojunction
Authors: Liu Xiaoyan , Zhu Jiaqi , Shan Yufeng , Liu Changlong , Pan Changyi , Zhang Tianning , Liu Chixian , Chen Tianye , Ling Jingwei , Duan Junli , Qiu Feng , Rahman Saqib , Deng Huiyong , Dai Ning
Published: October 2024

As unique building blocks for advancing optoelectronics, 2D semiconducting transition metal dichalcogenides have garnered significant attention. However, most previously reported MoS2 photodetectors respond only to visible light with limited absorption, resulting in a narrow spectral response and low sensitivity. Here, a surrounding homojunction MoS2 photodetector featuring localized p‐type nitrogen plasma doping on the surface of n‐type MoS2 while preserving a high‐mobility underlying channel for rapid carrier transport is engineered. The establishment of p‐n homojunction facilitates the efficient separation of photogenerated carriers, thereby boosting the device's intrinsic detection performance. The resulting photoresponsivity is 6.94 × 104 A W−1 and specific detectivity is 1.21 × 1014 Jones @ 638 nm, with an optimal light on/off ratio of ≈107 at VGS = −27 V. Notably, the introduction of additional bands within MoS2 bandgap through nitrogen doping leads to an extrinsic broadband response to short‐wave infrared. The device exhibits a photoresponsivity of 34 A W−1 and a specific detectivity of up to 5.92 × 1010 Jones @ 1550 nm. Furthermore, the high‐performance broadband response is further demonstrated through imaging and integration with waveguides, paving the way for next generation of multifunctional imaging systems and high‐performance photonic chips.
Au···I coinage bonds: Boosting photoluminescence efficiency and solid‐state molecular motion
Authors: Zhao Xueqian , Gong Junyi , Li Zikang , Sung Herman H. Y. , Williams Ian D. , Lam Jacky W. Y. , Zhao Zheng , Tang Ben Zhong , Wong Wai‐Yeung , Xu Linli
Published: October 2024

Coinage bonds, a type of noncovalent interaction, occur between group 11 elements (Au, Ag, and Cu) with electron donor groups. Despite theoretical validation, empirical evidence remains limited. In this study, an aggregation‐induced emission (AIE)‐active Au(I) complex, ITCPAu, which exhibits Au···I coinage bonds, was revealed based on the single‐crystal X‐ray diffraction and theoretical calculations. Further examination of the luminescence properties of the ITCPAu revealed multiswitchable behavior, including mechanochromism and thermochromism. Nearly pure white‐light emission was achieved with Commission Internationale de L'Eclairage (CIE) 1931 chromaticity coordinates of (0.30, 0.31) by grinding the green‐emissive ITCPAu monomer crystals. Moreover, visualization and manipulation of solid‐state molecular motion (SSMM) in the yellow‐emissive ITCPAu dimer crystals, driven by the robust Au···I coinage bonds, were revealed through a combination of crystal engineering and luminescent properties. Furthermore, to support the robust Au···I coinage bonds, a versatile carrier for small solvent molecules in crystal lattices was developed for uptake and release. Our findings provide experimental and theoretical evidence for Au···I coinage bonds, highlighting their ability to boost photoluminescence quantum yield (PLQY) and trigger SSMM, emphasizing their potential in developing smart materials with stimuli‐responsive properties.
APOE 𝜀4‐related blood–brain barrier breakdown is associated with microstructural abnormalities
Authors: Reas Emilie T. , Solders Seraphina K. , Tsiknia Amaryllis , Triebswetter Curtis , Shen Qian , Rivera Charlotte S. , Andrews Murray J. , Alderson‐Myers Austin , Brewer James B.
Published: October 2024

INTRODUCTION

Blood–brain barrier (BBB) dysfunction occurs in Alzheimer's disease (AD). Yet, the stage at which it appears along the AD time course and whether it contributes to neurodegeneration remain unclear.

METHODS

Older adults (61 to 90 years) from cognitively normal (CN) to mildly cognitively impaired (CI), enriched for APOE 𝜀4 and amyloid positivity, underwent dynamic contrast‐enhanced (DCE) magnetic resonance imaging (MRI) and diffusion MRI to measure BBB permeability and brain microstructure. Analysis of variance compared BBB permeability according to cognitive status, amyloid beta (Aβ), and APOE4. Linear regressions assessed associations of BBB permeability with brain microstructure and interactions with Aβ and APOE4.

RESULTS

BBB permeability was elevated for APOE4 carriers across the cortical gray matter, with the strongest differences among CN amyloid‐negative individuals. Associations between entorhinal BBB permeability and microstructure interacted with Aβ and APOE4, with the strongest relationships in amyloid‐positive individuals and APOE4 carriers.

DISCUSSION

APOE4 may drive widespread BBB dysfunction in preclinical AD, which may contribute to neurodegenerative changes early along the AD cascade.

Highlights

Gray matter blood–brain barrier (BBB) permeability is elevated for APOE4 carriers.

APOE4‐related BBB breakdown appears in the absence of cognitive decline or amyloid.

BBB leakage correlates with entorhinal cortex microstructural injury.

Associations with microstructure are strongest for amyloid‐positive APOE4 carriers.
The role of leukocytes in cognitive impairment due to long‐term exposure to fine particulate matter: A large population‐based mediation analysis
Authors: Aretz Benjamin , Doblhammer Gabriele , Heneka Michael T.
Published: October 2024

INTRODUCTION

Our understanding of how fine particulate matter (PM2.5) impacts cognitive functioning is limited. Systemic inflammation processes may play a role in mediating this effect.

METHODS

This prospective cohort study used data from 66,254 participants aged 18+ between 2006 and 2015 from the Dutch Lifelines Cohort Study and Biobank. Causal mediation analysis was conducted to examine the impact of ambient PM2.5 exposure on cognitive processing time (CPT), using the change in white blood cell (WBC) count and its subtypes as potential mediators.

RESULTS

Heightened PM2.5 exposure was associated with slower CPT (total effect = 81.76 × 10−3, 95% confidence interval [CI] 59.51 × 10−3–105.31 × 10−3). The effect was partially mediated via increased WBC count (indirect effect [IE] = 0.42 × 10−3, 95% CI 0.07 × 10−3–0.90 × 10−3), particularly driven by an increase in monocytes (IE = 0.73 × 10−3, 95% CI 0.24 × 10−3–1.31 × 10−3).

DISCUSSION

Systemic inflammation processes may partially explain the harmful effects of PM2.5 on cognitive functioning, why lower levels of systemic inflammation may help contain its neurotoxic effects.

Highlights

The pathways leading to the neurotoxic effects of fine particulate matter (PM2.5) are poorly understood.

We analyzed data from over 66,000 participants using causal pathway analysis.

Increased white blood cell (WBC) count mediates the effect of PM2.5 on cognitive functioning.

Monocyte count played a crucial role in this low‐pollution setting.

Systemic inflammation may contribute to the neurotoxic effects of PM2.5.
Serum Glial Fibrillary Acidic Protein and Neurofilament Light Chain Levels Reflect Different Mechanisms of Disease Progression under B‐Cell Depleting Treatment in Multiple Sclerosis
Authors: Benkert Pascal , Maleska Maceski Aleksandra , Schaedelin Sabine , Oechtering Johanna , Zadic Amar , Vilchez Gomez Juan Francisco , Melie‐Garcia Lester , Cagol Alessandro , Galbusera Riccardo , Subramaniam Suvitha , Lorscheider Johannes , Galli Edoardo , Mueller Jannis , Fischer‐Barnicol Bettina , Achtnichts Lutz , Findling Oliver , Lalive Patrice H. , Bridel Claire , Uginet Marjolaine , Müller Stefanie , Pot Caroline , Mathias Amandine , Du Pasquier Renaud , Salmen Anke , Hoepner Robert , Chan Andrew , Disanto Giulio , Zecca Chiara , D'Souza Marcus , Hemkens Lars G. , Yaldizli Özgür , Derfuss Tobias , Roth Patrick , Gobbi Claudio , Brassat David , Tackenberg Björn , Pedotti Rosetta , Raposo Catarina , Oksenberg Jorge , Wiendl Heinz , Berger Klaus , Hermesdorf Marco , Piehl Fredrik , Conen David , Buser Andreas , Kappos Ludwig , Khalil Michael , Granziera Cristina , Abdelhak Ahmed , Leppert David , Willemse Eline A.J. , Kuhle Jens ,   for the Swiss MS Cohort study (SMSC)
Published: October 2024

Objective

To investigate the longitudinal dynamics of serum glial fibrillary acidic protein (sGFAP) and serum neurofilament light chain (sNfL) levels in people with multiple sclerosis (pwMS) under B‐cell depleting therapy (BCDT) and their capacity to prognosticate future progression independent of relapse activity (PIRA) events.

Methods

A total of 362 pwMS (1,480 samples) starting BCDT in the Swiss Multiple Sclerosis (MS) Cohort were included. sGFAP levels in 2,861 control persons (4,943 samples) provided normative data to calculate adjusted Z scores.

Results

Elevated sGFAP levels (Z score >1) at 1 year were associated with a higher hazard for PIRA (hazard ratio [HR]: 1.80 [95% CI: 1.17–2.78]; p = 0.0079) than elevated sNfL levels (HR, 1.45 [0.95–2.24], p = 0.0886) in a combined model. Independent of PIRA events, sGFAP levels longitudinally increased by 0.49 Z score units per 10 years follow‐up (estimate, 0.49 [0.29, 0.69], p < 0.0001). In patients experiencing PIRA, sGFAP Z scores were 0.52 Z score units higher versus stable patients (0.52 [0.22, 0.83], p = 0.0009). Different sNfL Z score trajectories were found in pwMS with versus without PIRA (interaction p = 0.0028), with an average decrease of 0.92 Z score units per 10 years observed without PIRA (−0.92 [−1.23, −0.60], p < 0.0001), whereas levels in patients with PIRA remained high.

Interpretation

Elevated sGFAP and lack of drop in sNfL after BCDT start are associated with increased risk of future PIRA. These findings provide a rationale for combined monitoring of sNfL and sGFAP in pwMS starting BCDT to predict the risk of PIRA, and to use sGFAP as an outcome in clinical trials aiming to impact on MS progressive disease biology. ANN NEUROL 2025;97:104–115
π‐Komplexe aus Nicht‐Klassischen Diboriranen: Side‐on vs. End‐on Carbonylierende Ringerweiterung
Authors: Grewelinger Philipp , Präsang Carsten , Zimmer Michael , Morgenstern Bernd , Scheschkewitz David
Published: October 2024

Im Gegensatz zu Cyclopropanen neigen die analogen B2C‐Spezies (Diborirane) dazu, nicht‐klassische Hückel‐aromatische Strukturen mit verbrückenden Resten R zwischen den Boratomen auszubilden. Die Koordination des so erzeugten zyklischen 2e− π‐Systems an Übergangsmetalle ist völlig unerforscht. Wir berichten, dass die Komplexierung von nicht‐klassischen Diboriranen cyclo‐μ‐RB2Dur2CPh (R=H, SnMe3; Dur=2,3,5,6‐Tetramethylphenyl) mit Fe(CO)3‐Fragmenten eine carbonylierende Ringerweiterung des B2C‐Rings zu vier‐ oder fünfgliedrigen Ringen ermöglicht, abhängig von der Art der BRB‐3‐Zentren‐2‐Elektronenbindung (3c2e): Das H‐verbrückte Diboriran (R=H) reagiert zunächst mit Fe2(CO)9 zum allylischen π‐Komplex mit einer agostischen BH/Fe‐Wechselwirkung. Die anschließende formale Hydroborierung von CO aus überschüssigem Fe2(CO)9 führt zur side‐on Ringerweiterung unter Ausbildung eines fünfgliedrigen B2C2O‐Rings, der an eine Fe(CO)3‐Einheit koordiniert ist. Im Gegensatz dazu wird im Falle des stannylverbrückten Diborirans (R=SnMe3) unter denselben Bedingungen CO endständig an die B−B‐Bindung addiert, wobei das Kohlenstoffende formal in die B2Sn 3c2e‐Bindung insertiert. Die beiden carbonylierenden Ringerweiterungsprodukte können auch als nido‐ bzw. closo‐Cluster nach den Wade‐Mingos‐Regeln beschrieben werden.
Solvation Effect‐Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts
Authors: Liu Shangheng , Wang Xiaocan , Huang Wei‐Hsiang , Zhang Qiugen , Han Jiajia , Zhang Yingtian , Pao Chih‐Wen , Hu Zhiwei , Xu Yong , Huang Xiaoqing
Published: October 2024

Cation exchange (CE) reaction is a classical synthesis method for creating complex structures. A lock of study on intrinsic mechanism limits its understanding and practical application. Using X‐ray absorption spectroscopy, we observed that the evolution from Ru−Cl to Ru−O/OH occurs during the CE between K2RuCl6 and CoSn(OH)6 in aqueous solution, while CE between K2PtCl6 and CoSn(OH)6 is inhibited due to the failure of structural evolution from Pt−Cl to Pt−O/OH. Theoretical simulations imply that the interaction between Ru−O and CoSn(OH)6 with Co vacancy (CoVCoSn(OH)6) endows the electron transfer, as a result of strengthened adsorption on CoVCoSn(OH)6. Moreover, this mechanism is validated for CE between K2RuCl6 and ASn(OH)6 (A=Mg, Ca, Mn, Co, Cu, Zn), and CE between K2PdCl6/Na3RhCl6/K2IrCl6 and CoSn(OH)6. Impressively, the Pt‐free CoRuSn(OH)x produced via CE displays a mass activity and a power density of 15.0 A mgRu−1 and 11.6 W mgRu−1, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mgRu+Pt−1 and 9.0 W mgRu+Pt−1). This work, for the first time, reveals the intrinsic mechanism of CE as structural evolution of target ion breaking through the traditional classic etch‐adsorption mechanism and will promote fundamental research and practical application in various fields.
Integrated Omnidirectional Design of Non‐Volatile Solid Additive Enables Binary Organic Solar Cells with Efficiency Exceeding 19.5 %
Authors: Wang Ya‐Ting , Sun Wen‐Jing , Zhang Yamin , Zhang Bo‐Yang , Ding Yun‐Tao , Zhang Ze‐Qi , Meng Lingxian , Huang Kexin , Ma Wei , Zhang Hao‐Li
Published: October 2024

Solid additives have drawn great attention due to their numerous appealing benefits in enhancing the power conversion efficiencies (PCEs) of organic solar cells (OSCs). To date, various strategies have been reported for the selection or design of non‐volatile solid additives. However, the lack of a general design/evaluation principles for developing non‐volatile solid additives often results in individual solid additives offering only one or two efficiency‐boosting attributes. In this work, we propose an integrated omnidirectional strategy for designing non‐volatile solid additives. By validating the method on the 4,5,9,10‐pyrene diimide (PyDI) system, a novel non‐volatile solid additive named PyMC5 was designed. PyMC5 is capable of enhancing device performance by establishing synergistic dual charge transfer channels, forming appropriate interactions with active layer materials, reducing non‐radiative voltage loss and optimizing film morphology. Notably, the binary device (PM6 : L8‐BO) treated by PyMC5 achieved a PCE over 19.5 %, ranking among the highest reported to date. In addition, the integration of PyMC5 mitigated the degradation process of the devices under photo‐ and thermal‐stress conditions. This work demonstrates an efficient integrated omnidirectional approach for designing non‐volatile solid additives, offering a promising avenue for further advancements in OSC development.
Solvent Polarity‐Induced Regulation of Cation Solvation Sheaths for High‐Voltage Zinc‐Based Batteries with a 1.94 V Discharge Platform
Authors: Jin Xuting , Lai Guobin , Xiu Xinyi , Song Li , Li Xiangyang , Dai Chunlong , Li Meng , Quan Zhonggui , Tang Bin , Shao Gonglei , Zhang Zhipan , Liu Feng , Qu Liangti , Zhou Zhen
Published: October 2024

To address the challenge of low discharge platforms (<1.5 V) in aqueous zinc‐based batteries, highly concentrated salts have been explored due to their wide electrochemical window (~3 V). However, these electrolytes mainly prevent hydrogen evolution and dendrite growth at the anode without significantly enhancing voltage performance. Herein we introduce an approach by adjusting solvent polarity to regulate cation solvation sheaths in hybrid electrolytes, reducing Zn/Zn2+ oxidation potential and water activity. Through strong cation‐water coordination and hydrogen bonding between dimethylsulfoxide and water, the designed electrolyte, at a low concentration, achieves a broader electrochemical window (4 V) than conventional concentrated electrolytes. Using this electrolyte, a Zn/Zn battery showed an impressive cycle life of 4340 cycles, while a Zn/lithium manganate battery delivered a high discharge platform of over 1.9 V with exceptional cycling stability. A Zn‐based micro‐battery with a polyvinyl alcohol‐based hybrid electrolyte also achieved a record‐high discharge platform of 1.94 V. This work presents a promising strategy for developing low‐concentration electrolytes for high‐performance sustainable energy storage.
Adjustment of temperature sensitivity using hydrophilic materials to develop superabsorbent polymers based on poly(N‐isopropyl acrylamide) as a temperature‐sensitive material
Authors: Chen Diming , Ou Baoli , Ma Lifang
Published: October 2024

Poly(N‐isopropyl acrylamide) (PNIPAm) is a temperature‐sensitive material with a fast temperature response and a low critical solubilization temperature (LCST) of approximately 32°C, but it swells only 20–40 times after absorbing water. To enhance its water‐absorption properties, we introduced hydrophilic monomers into the NIPAm monomer to prepare a ternary copolymerized superabsorbent polymer. In addition, we characterized this copolymer using various techniques and analyzed its temperature‐sensitive and water‐absorbing properties. The results showed that the optimal synthesis conditions consisted of m(NIPAm):m(AMPS) = 4, 1.5% initiator, 0.3% cross‐linking agent, and 1.0% quaternized ammonium chitosan, which ensured the significant temperature sensitivity of the water‐absorbent resin. Under these conditions, the swelling ratio of the water‐absorbing resin reached 235.3 times, the LCST value was 44.6°C, the water retention rate was 84.9% at 25°C after 12 h, and the shrinkage ratio reached 81.7% at 60°C after 3 h, and 97.6% after 12 h. The resulting material could be rapidly dehydrated at high temperatures and presented clear temperature‐sensitive characteristics while maintaining excellent water‐absorbing properties.
Interceptive abilities in autism spectrum disorder: Comparing naturalistic and virtual visuomotor tasks
Authors: Park Se‐Woong , Cardinaux Annie , Crozier Dena , Russo Marta , Bond Sabrina , Kjelgaard Margaret , Sinha Pawan , Sternad Dagmar
Published: October 2024

A growing body of research reveals that autistic individuals exhibit motor coordination challenges. Multiple theoretical frameworks propose that the seemingly disparate features of autism may arise from a common underlying process: a diminished ability to make predictions. Sensorimotor skills, such as catching a ball, critically rely on predicting the ball's trajectory as well as anticipatory coordination of the entire body. Here, we assessed four different naturalistic and virtual interception tasks with 31 neurotypical and 23 autistic children (ages 7–12). In a naturalistic setting, participants caught the ball either with their hands or a hand‐held funnel with an enlarged catch area that also prevented the ball from bouncing off. A virtual setup reduced whole‐body demands, as children only moved a paddle to catch or bounce a ball on a screen. Control tasks, involving rapid reaching to grasp a static object and quiet standing, which largely eliminated the requirements for prediction, were also tested. Results from all task variations demonstrated that autistic children completed fewer successful interceptions, suggesting that predictive requirements, inherent to all interception tasks, played a critical role. Effect sizes in the virtual tasks were smaller. Correlations of the task metrics with behavioral assessments rendered the strongest correlations with Praxis scores. The control tasks showed no differences between autistic and neurotypical children. These findings lend support to the emerging hypothesis that predictive challenges are present in autism. Further research with larger sample sizes will help identify to what extent these visuomotor differences may inform core domains of autism.
Prenatal exposure to hypoxic risk conditions in autistic and neurotypical youth: Associated ventricular differences, sleep disturbance, and sensory processing
Authors: Preciado Cristian , Baida Maria , Li Yi , Li Yan , Demopoulos Carly
Published: October 2024

There is a growing body of research that suggests conditions during the period of pregnancy and birth can affect how autism spectrum disorder (ASD) presents itself. This study aimed to investigate the incidence of oxygen deprivation during this period known as prenatal and perinatal hypoxic risk (HR) conditions in ASD compared with neurotypical control (NTC) youth. We also examined ventricular morphology variations associated with HR exposure, and to evaluate associations with clinical symptoms. Results from a cohort of 104 youth revealed a higher incidence of exposure to prenatal hypoxic conditions in the ASD group. Additionally, ASD individuals with prenatal hypoxic exposure (ASD + HR) demonstrated larger third ventricle volumes compared with both ASD and NTC individuals without such exposure (ASD‐HR and NTC‐HR, respectively). Furthermore, associations were identified between prenatal hypoxic exposure, third ventricle volume, sensory dysfunction, and severity of sleep disturbances. These findings suggest exposure to prenatal hypoxic risk conditions may exacerbate or modify the neurodevelopmental trajectory and symptom severity in ASD, emphasizing the need for better prenatal care and specific interventions to reduce these risks.
Electrolyte‐free cathode design for solid‐state batteries demonstrated with bifunctional Li2VCl4
Authors: Kasahara Takuma , Song Peng , Honma Itaru , Ohno Saneyuki
Published: October 2024

All‐solid‐state batteries have attracted much attention because of the expected high energy density and inherent safety stemming from their nonflammable property. While improving the energy density of the cathode poses a significant challenge, here we introduce a novel battery design strategy to enhance energy density by employing bifunctional cathode material, allowing the weight ratio of the active material to be increased without using an electrolyte for the cathode. By employing lithium‐containing vanadium halide Li2VCl4, serving as both active material and electrolyte, the all‐solid‐state battery cell with no electrolyte for the cathode with a capacity approaching the theoretical limit is demonstrated. In addition, we present a guideline for improving capacity retention from the perspective of interfacial stability. Notably, thermodynamic analysis revealed interfacial instability between Li2VCl4 and sulfide material. A double‐layer separator, incorporating halide materials for the cathode side, was implemented to enhance the interfacial stability and mitigate the capacity degradation. Furthermore, it was found that the rate capability depends on the lithium content in synthesized Li2‐xVCl4 and does not change with the state of charge significantly. This study will contribute to designing the bifunctional cathode material for an all‐solid‐state battery and describe its unique properties.
Transcriptional Downregulation of Methanol Metabolism Key Genes During Yeast Death in Engineered Pichia pastoris
Authors: Wang Chenbo , Jiang Wei , Yu Chang , Xia Jianye
Published: October 2024

Pichia pastoris possesses the unique ability to utilize methanol as its sole carbon source, which makes it a proper host for producing various high‐value‐added products via metabolic engineering. Nevertheless, cell death has been observed during the fermentation of modified P. pastoris, with limited literature elucidating the underlying causes and mechanisms. Understanding the death mechanisms during methanol‐based fermentation is crucial for optimizing fermentation strategies, enhancing the accumulation of target products, and reducing production costs. Here, we first sought to eliminate the potential causes of cell death during fermentation, such as inadequate inorganic salts and toxic by‐product accumulation. The elimination of these potential causes was achieved efficiently utilizing the high‐throughput fermentation equipment. Subsequently, we established a correlation between yeast cell death and the duration of the methanol metabolism period by monitoring the growth of the yeast at different fermentation stages. A critical revelation from this work came from analyzing the yeast's transcriptomic data at various stages of methanol metabolism. It was observed that a significant characteristic of yeast cell death during fermentation was the marked down‐regulation of transcript levels of key enzymes involved in the methanol assimilation pathway and genes related to their biosynthesis process. The findings of this work are crucial for better understanding the causes and mechanisms of cell death for engineered P. pastoris during methanol‐utilized fermentation.
Do gender diversity and foreign investor affect sustainability disclosure
Authors: Widjaja Jahja Hamdani , Joni Joni , Riyanto Naomi Fani
Published: October 2024

We examine the effect of female board members and foreign institutional investors on corporate social responsibility (sustainability) disclosure in Indonesian listed firms from 2015 to 2017. Our final sample comprised 1192 firm‐year observations. We apply ordinary least squares pool regression to estimate the associations and address the endogeneity problem using the two‐stage least squares model, generalized method of moments, and lagged variables. While previous studies have focused on the impact of female board members and foreign institutional investors on financial outcomes, we extend the literature by investigating the association between both female board members and foreign investors and sustainable disclosure in Indonesia, where the participation of women is nominal, especially at the top management level, and the level of foreign ownership is high. Our findings propose a proportion of women as board members for listed firms and promote attractive policies to increase the number of foreign investors investing in Indonesia. It also contributes to conflicting results regarding the relationship between corporate governance and corporate social responsibility (CSR) commitment. Our results were robust after testing for endogeneity and adding more control variables. Overall, the findings have practical implications for policymakers and investors regarding corporate disclosure and governance in Indonesia.
Sustainable development and firm value: How ESG performance shapes corporate success—a systematic literature review
Authors: Li Xuan , Saat Maisarah Mohamed , Khatib Saleh F. A. , Liu Yang
Published: October 2024

This study is designed to conduct a systematic literature review aimed at assessing the influence of environmental, social, and governance (ESG) performance on firm value. Although previous studies have explored their relationship, a comprehensive systematic review on this topic is still lacking. We conducted a detailed literature search in the Scopus and Web of Science databases and identified 73 papers published between 2016 and 2023 as the sample, covering annual trends, country and industry distribution, theoretical frameworks, proxy variables, research methods, research results, and provided direction for future research. We found a significant increase in the number of studies over the past 3 years. Cross‐country studies dominated the field, with most research adopting multi‐industry analysis, while studies focusing on a single industry were relatively rare. The stakeholder theory and agency theory were the most widely applied theories. Most studies showed that ESG performance had a positive effect on firm value, reflecting the growing importance that markets and investors placed on ESG performance and its contribution to long‐term firm growth. However, some studies reported negative or insignificant effects, noting that the effects of ESG performance varied by industry, region, and market environment. This study suggests that future research should explore the independent and interactive effects of each ESG dimension on firm value, focusing on dynamic relationships across industries and regions, using new methods and models, and incorporating moderating variables. This study provides practical guidance for firm managers and policymakers to optimize ESG practices, enhancing firm value and promoting sustainability.
Thiazepine‐Based Hybrids as Promising Anti‐Colon Cancer Agents: Design, Synthesis, Computational and In Vitro Screening
Authors: Vaghasiya Mahesh D. , Sain Arindam , Mendapara Jigarkumar V. , Khamrai Dipshikha , Naskar Debdut , Kumari Premlata
Published: October 2024

Novel thiazepine‐based hybrids (9 a–d) were designed and synthesized to create lead molecules with exceptional anti‐colon cancer efficacy. Analytical methods, including IR, NMR, and HR‐MS, characterized the synthesized compounds. The in vitro colorectal study was carried out to compare the biological activity of newly developed compounds with the computational data. The tested compounds induced cytotoxicity in HT‐29 cells for both 24 h and 48 h in a dose‐dependent manner. However, compound 9 a induced cytotoxicity at much higher concentrations compared to the rest of the compounds. 9 b and 9 c caused 50 % cell death (compared to the untreated cells) at a dose of ~50 μM and 40 μM in case of 24‐hour exposure, respectively. On the contrary, for 48 h exposure, both 9 b and 9 c induced 50 % cell death concerning untreated cells at a dose of around ~20 μM, whereas 9 d exhibited 50 % cell death at 5 μM in the case of 48 h exposure. In silico ADMET was also carried out to understand the pharmacokinetics and safety profiles of the drug candidates. We found some of the critical targets of these compounds, which eventually will be integral to exploring the mechanistic actions of these compounds in colon cancer.
Optimizing Activity and Stability in AgCl‐CuO Electrocatalysts: Insights from Different Morphologies for Enhanced ORR Performance
Authors: Yatheendran Anagha , Nachimuthu Koushik Kumar , George Ashna , Sandhyarani N.
Published: October 2024

Highly enduring and methanol‐tolerant electrocatalysts are pertinent to revolutionizing direct methanol fuel cell (DMFC) technologies. Transition‐metal‐based electrocatalysts are anticipated to rank among the remarkable electrocatalysts for boosting the sluggish oxygen reduction reaction (ORR) kinetics. In this study, we report a facile approach to optimize the activity and stability of the AgCl‐CuO systems. The tailored nanoparticle–nanorod (NP–NR) and nanoleaf (NL) like morphologies deliver remarkable bifunctional catalytic performance for oxygen reduction and hydrogen evolution reactions, sustained activity, and comparatively better stability for ORR. A meager shift of only 0.014 and 0.024 V in the half‐wave potential is observed in the NP‐NR and NL structures, respectively, for the ORR even after 2500 cycles. Furthermore, both the AgCl‐CuO composite exhibit an excellent tolerance to methanol.
Structural Regulation of a Multi‐Component Co2P2O7‐MoN/NC Electrocatalyst for Efficient Oxygen Evolution Reaction
Authors: Jin Man , Zou Yan , Shi Bo‐Cong , Tang Yu‐Jia , Liu Ting‐Ting , Liu Li‐Ming , Geng Dongsheng
Published: October 2024

Realizing efficient and durable non‐precious metal‐based electrocatalysts for oxygen evolution reaction (OER) still remains a great challenge. Here, a multi‐component composite of Co2P2O7‐MoN/NC containing pyrophosphate, nitride, and nitrogen‐doped carbon is successfully prepared via a facile two‐step synthesis method. Combining the structural regulation between the active metal‐ and non‐metal‐based species, Co2P2O7‐MoN/NC demonstrates superior activity and durability for OER, requiring an overpotential of 278 mV at a current density of 10 mA cm−2, a Tafel slope of 83.3 mV dec−1, and long‐term stability over 100 h in an alkaline solution. Post‐characterizations reveal that synergistic effect among stable Co2P2O7, partially dissolved MoN, N‐doped carbon, and new‐formed CoOOH nanosheets enable structural reconstruction, fast charge transfer, and formation of oxygen‐containing intermediates, promoting the OER performance significantly. This work provides a promising pathway to tune multi‐components to fabricate efficient transition‐metal‐based electrocatalysts in energy conversion applications.
Tumor Cell‐Specific Metabolic Labelling of Surface Sialoglycans and Post‐Click with Multivalent Rhamnose Enable Precise Immune Killing by Endogenous Antibody
Authors: Hong Haofei , Li Yanchun , Li Dan , Lin Han , Zhao Jie , Wang Zheng , Wu Zhimeng
Published: October 2024

Comprehensive Summary

We report the design and development of a β‐glucuronidase (β‐Glu)‐responsive ManNAz derivative, Glu‐AAM, for tumor‐selective metabolic glycoengineering. Glu‐AAM enables specific labeling of tumor cell surface sialoglycans in the presence of overexpressed β‐Glu in cancer cells, including breast, leukemia, and colorectal cancer cells. We demonstrate the high selectivity and efficiency of Glu‐AAM‐mediated metabolic glycoengineering across multiple cancer cell lines. Furthermore, we synthesized multivalent antibody‐recruiting molecules (DBCO‐Rha) that can be covalently attached to the azido‐modified tumor cell surface, leading to potent antibody‐dependent cellular phagocytosis and complement‐dependent cytotoxicity. The octameric DBCO‐Rha8 construct exhibited the most effective immune response. This integrated strategy of β‐Glu‐responsive metabolic glycoengineering and antibody‐recruiting immunotherapy provides a promising platform for targeted cancer therapies and expands the toolbox of metabolic glycoengineering for cancer immunotherapy.
Metastatic Upper Thoracic Intramedullary Spinal Cord Tumor of Ovarian Adenocarcinoma: A Rare Case Report and Literature Review
Authors: Heidari Vahid , Mollahoseini Reza , Golchin Navid , Karimi Hadi , Hoseini Mohammad , Kazemi Benyamin , Zolfeghari Elmira , Ashayeri Ahmadabad Hemin
Published: October 2024

Background

Intramedullary spinal cord metastasis (ISCM) is uncommon and usually occurs in advanced malignancies. Effective management methods are not clearly defined, and the outcomes of current treatments vary. Currently, there is no universal strategy for managing patients with intramedullary spinal metastases.

Case

To the best of our knowledge, we present a case of ovarian adenocarcinoma that was managed surgically in a 70‐year‐old woman with metastasis to the upper thoracic spinal cord, and we assess pertinent literature and deliberate management approaches.

Conclusions

Progression in early diagnosis and advanced therapeutic methods for ISCMs have contributed to the increased incidence and prevalence of this condition. There is no established consensus regarding the definitive patient management methods. Consequently, we offer multidisciplinary management with individualization based on the patient's functional status, requirement for a definitive diagnosis for potential additional adjuvant therapies, and assessment of the extent of systemic disease, which can influence the desired quality of life and survival duration.