bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cross‐Linker Architectures Impact Viscoelasticity in Dynamic Covalent Hydrogels
Authors: Lin Yung‐Hao , Lou Junzhe , Xia Yan , Chaudhuri Ovijit 
Published: October 2024

AbstractDynamic 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

AbstractPlasmonic 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

AbstractPerfect 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

AbstractLead 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

AbstractSix‐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

AbstractConstructing 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

AbstractPhotosensitizers 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

AbstractNon‐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

AbstractAs 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

AbstractCoinage 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

AbstractINTRODUCTIONBlood–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.METHODSOlder 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.RESULTSBBB 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.DISCUSSIONAPOE4 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

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

ObjectiveTo 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.MethodsA 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.ResultsElevated 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.InterpretationElevated 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

AbstractIm 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.