bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evolution and Reconstruction of Air‐Electrode Surface Composition in Reversible Protonic Ceramic Cells: Mechanisms, Impacts on Catalytic Performance, and Optimization Strategies – A Review
Authors: Shi Nai , Xie Yun , Tadé Moses Oludayo , Shao Zongping 
Published: February 2025

AbstractReversible protonic ceramic cells (R‐PCCs) are at the forefront of electrochemical conversion devices, capable of reversibly and efficiently converting chemical energy into electricity at intermediate temperatures (350–700 °C) with zero carbon emissions. However, slow surface catalytic reactions at the air‐electrode often hinder their performance and durability. The electrode surface is not merely an extension of the bulk structure, equilibrium reconstruction can lead to significantly different crystal‐plane terminations and morphologies, which are influenced by material's intrinsic properties and external reaction conditions. Understanding electrode surface evolution at elevated temperatures in water‐containing, oxidative atmospheres presents significant importance. In this review, a comprehensive summary of recent processes in applying advanced characterization techniques for high‐temperature electrode surfaces is provided, exploring the correlations between surface evolution and performance fluctuations by examining the structural evolution and reconstruction of various air‐electrode surfaces associated with degradation and activation phenomena, offering insights into their impact on electrode performance. Furthermore, reported strategies and recent advances in enhancing the electrochemical performance of R‐PCCs through engineering air‐electrode surfaces is discussed. This review offers valuable insights into surface evolution in R‐PCCs and is expected to guide future developments in high‐temperature catalysis, solid‐state ionics, and energy materials.
A Wireless Operated Flexible Bioelectronic Microneedle Patch for Actively Controlled Transdermal Drug Delivery
Authors: Jin Taosha , Wang Haiyang , Ullah Ihsan , Xie Wenjiao , Lin Taian , Tan Qiaoling , Pan Xiaoyu , Yuan Youyong 
Published: February 2025

AbstractPrecise control over drug release rates is critical for enhancing therapeutic efficacy, reducing side effects, and maintaining stable drug levels. While microneedles (MNs) offer a promising approach for transdermal drug delivery, conventional passive‐response systems often lack adaptability across diverse drugs and disease models, limiting their versatility. Here, this work presents a flexible bioelectronic microneedle patch (FBMP) that integrates flexible electronics for actively controlled transdermal delivery. The FBMP incorporates a flexible printed circuit board (FPCB), a eutectic gallium‐indium (EGaIn) heating film, and dual‐layer microneedles with a polyvinyl alcohol (PVA) core and polycaprolactone (PCL) shell. This configuration allows real‐time adjustment of the thermal response rate via smartphone‐controlled Bluetooth, achieving rapid drug release within 2 min or sustained release over 10 h. In various animal models, the FBMP demonstrate versatility in delivering multiple drug types, optimizing efficacy, and minimizing side effects for both acute and chronic conditions. Overall, this work introduces a flexible, universal electronic microneedle platform with significant potential to advance precision and personalized medicine by enabling customizable, actively controlled drug release.
Myocardia‐Injected Synergistically Anti‐Apoptotic and Anti‐Inflammatory Poly(amino acid) Hydrogel Relieves Ischemia‐Reperfusion Injury
Authors: Luo Qiang , Li Zhibo , Sun Wei , Wang Guoliang , Yao Haochen , Wang Guoqing , Liu Bin , Ding Jianxun 
Published: February 2025

AbstractReperfusion therapy is the most effective treatment for acute myocardial infarction, but its efficacy is frequently limited by ischemia‐reperfusion injury (IRI). While antioxidant and anti‐inflammatory therapies have shown significant potential in alleviating IRI, these strategies have not yielded satisfactory clinical outcomes. For that, a thermo‐sensitive myocardial‐injectable poly(amino acid) hydrogel of methoxy poly(ethylene glycol)45‐poly(L‐methionine20‐co‐L‐alanine10) (mPEG45‐P(Met20‐co‐Ala10), PMA) loaded with FTY720 (PMA/FTY720) is developed to address IRI through synergistic anti‐apoptotic and anti‐inflammatory effects. Upon injection into the ischemic myocardium, the PMA aqueous solution undergoes a sol‐to‐gel phase transition and gradually degrades in response to reactive oxygen species (ROS), releasing FTY720 on demand. PMA acts synergistically with FTY720 to inhibit cardiomyocyte apoptosis and modulate pro‐inflammatory M1 macrophage polarization toward anti‐inflammatory M2 macrophages by clearing ROS, thereby mitigating the inflammatory response and promoting vascular regeneration. In a rat IRI model, PMA/FTY720 reduces the apoptotic cell ratio by 81.8%, increases vascular density by 34.0%, and enhances left ventricular ejection fraction (LVEF) by 12.8%. In a rabbit IRI model, the gel‐based sustained release of FTY720 enhanced LVEF by an additional 7.2% compared to individual treatment. In summary, the engineered PMA hydrogel effectively alleviates IRI through synergistic anti‐apoptosis and anti‐inflammation actions, offering valuable clinical potential for treating myocardial IRI.
Tailoring of Creep Regime Domain Wall Dynamics in Perpendicularly Magnetized Pd/Co/Pd Trilayers
Authors: Keloth Anurag , Raj Rakhul , Reddy V. Raghavendra , Gupta Mukul , Carlomagno Ilaria , Gloskovksii Andrei , Kuschel Timo , Gupta Ajay , Koyiloth Vayalil Sarathlal 
Published: February 2025

AbstractUnderstanding magnetic domain wall (DW) dynamics is vital for improving the performance of heavy metal/ferromagnet based spintronic devices. Pd/Co/Pd multilayers hosting perpendicular magnetic anisotropy and interfacial Dzyaloshinskii‐Moriya interaction are prototypes for high density magnetic memory devices. This work presents the creep regime DW dynamics in Pd/Co/Pd trilayers with Ta buffer layer excited by symmetric field‐induced domain wall motion using Kerr microscopy. A systematic increment of DW velocity with increasing Co thickness is observed. SQUID‐VSM measurements reveal that the effective anisotropy constant decreases with the Co layer, leading to an increased DW width. Kerr microscopy images confirm that the DW is becoming rougher with magnetic layer thickness because of the dominance of magnetostatic energy over the DW energy. Hard X‐ray photoemission spectroscopy (HAXPES) reveals the presence of alloying at interfaces of Co/Pd. The asymmetry in magnetic circular dichroism HAXPES at the Pd 3d edge pictures the induced magnetic moment in Pd which is consistent with the larger saturation magnetization obtained from vibrating sample magnetometry. Extended X‐ray absorption fine structure performed in out‐of‐plane and in‐plane geometry shows the disordered nature of the Co local environment with the interdiffusion of Pd atoms into Co causing an asymmetry in the bonds.
Second‐Generation One‐Pot Enantioselective Heck‐Matsuda Arylations of Unactivated Olefins Directly from Anilines and Nitroarenes
Authors: Melchior de Oliveira Leão Luiz Paulo , de Oliveira Valdeir Carlos , Henrique Duarte Chorro Tomaz , Aleksandrovich Gorbatov Sergei , Roque Duarte Correia Carlos 
Published: February 2025

AbstractA highly improved second generation of the one‐pot enantioselective Heck‐Matsuda reaction directly from anilines and nitroarenes is reported. This practical arylation method, featuring 56 examples, relies on the in situ diazotization of anilines and 3‐aminothiophenes, or from the in situ reduction‐diazotization of nitrobenzene derivatives. The in situ diazotization of the aniline, directly or from the in‐situ reduction of the nitroarene, synchronizes smoothly with the enantioselective Heck‐Matsuda reaction under mildly acidic conditions, bypassing the synthesis and handling of some unstable and/or difficult‐to‐prepare arenediazonium salts. The protocol was applied to the desymmetrization of unactivated olefins leading to the synthesis of functionalized spirocyclopentenyl hydantoins, aryl cyclopentenes, and β‐aryl‐γ‐lactones, in high yields (up to 99%) and er (up to 99:1). The efficiency of the method is showcased by the formal total synthesis of the bioactive compound VPC01091, a potential drug candidate for multiple sclerosis treatment at the gram scale in excellent yield (94%), in 97:3 er and 20>1 dr.
Scalable All‐Vacuum‐Processed Perovskite Solar Cells Enabled by Low Energy‐Disorder Hole‐Transport Layer
Authors: Choi Yunseong , Ma Hayoung , Jung Seungon , Jang Yunjeong , Kim Yujin , Kim Jiha , Jeong Mingyu , Lee Seunglok , Yang Sangjin , Hong Keun Kee , Lu Jianfeng , Yang Changduk , Park Hyesung 
Published: February 2025

AbstractAs perovskite solar cells (PSCs) require higher standards for commercial applications, all vacuum‐processed PSCs should become a key in future manufacturing processes of scalable PSCs compared to their currently dominating research types based on solution processes. In fact, vacuum deposition of high‐quality organic hole‐transport layers (HTLs) is crucial for successful fabrication of all vacuum‐processed scalable PSCs. Here, the study develops a triarylamine‐based single oligomer (TAA‐tetramer)−a miniaturized‐molecular form of the well‐known poly(triarylamine) (PTAA)−as a vacuum‐processable HTL in inverted PSCs. The well‐defined structure and monodisperse nature of the TAA‐tetramer render strong intermolecular π−π interactions and/or molecular ordering, resulting in simultaneously enhanced quasi‐Fermi level splitting and hole‐transport efficiency of the perovskite. The resulting all‐vacuum‐processed inverted PSCs exhibits a high power conversion efficiency (PCE) of 23.2%, which is record‐high performance reported among all‐vacuum‐processed PSCs, with exceptional device stabilities. Furthermore, the all‐vacuum‐deposition process allows the fabrication of efficient PSCs and modules with reliable scalability and minimized efficiency loss during scale‐up. Notably, the proposed HTL enabled high‐efficiency large‐area (25 cm2) single‐PSC with a PCE of 12.3%, representing one of the largest active areas and the highest performance ever reported for the large‐area device. A promising strategy for developing efficient, stable, and scalable PSCs for all‐vacuum processes is presented.
Why Didn't the Sifaka Cross the Road? Divergence of Propithecus edwardsi Gut Microbiomes Across Geographic Barriers in Ranomafana National Park, Madagascar
Authors: Donohue Mariah E. , Lamb Alicia , Asangba Abigail E. , Noromalala Eliette , Weisenbeck David R. , Stumpf Rebecca M. , Wright Patricia C. 
Published: February 2025

ABSTRACTThis study uses a biogeographic framework to identify patterns of gut microbiome divergence in an endangered lemur species endemic to Madagascar's southeastern rainforests, the Milne‐Edwards's sifaka (Propithecus edwardsi). Specifically, we tested the effects of (1) geographic barriers, (2) habitat disturbance, and (3) geographic distance on gut microbiome alpha and beta diversity. We selected 10 social groups from 4 sites in Ranomafana National Park with varied histories of selective logging. Sites were spaced between 4 and 17 km apart falling on either side of two parallel barriers to animal movement: the Namorona River and the RN25 highway. Using 16S rRNA metabarcoding, we found the greatest beta diversity differentiation to occur between social groups, with significant divisions on opposite sides of geographic barriers (road/river). Habitat disturbance had the most significant effect on alpha diversity, though, contrary to many other studies, disturbance was associated with higher microbial species richness. Without biomedical context, it is unclear whether microbiome differences observed herein are neutral, adaptive, or maladaptive. However, microbiome divergence associated with the road/river may be a symptom of reduced host gene flow, warranting further investigation and perhaps conservation action (e.g., construction of wildlife bridges). Finally, this work demonstrates that significant microbiome variation can accrue over small sampling areas, lending new insight into host‐microbe‐environmental interactions.
The miR‐6779/XIAP axis alleviates IL‐1β‐induced chondrocyte senescence and extracellular matrix loss in osteoarthritis
Authors: Li Zongchao , Dai Aonan , Fang Xiaoxiang , Tang Kexing , Chen Kun , Gao Peng , Su Jingyue , Chen Xin , Yang Shengwu , Deng Zhenhan , Li Liangjun 
Published: February 2025

AbstractBackgroundOsteoarthritis (OA) is a long‐term degenerative joint disease worsening over time. Aging and chondrocyte senescence contribute to OA progression. MicroRNAs have been confirmed to regulate different cellular processes. They contribute to OA pathology and may help to identify novel biomarkers and therapies for OA.MethodsThis study used bioinformatics and experimental investigations to analyze and validate differentially expressed miRNAs in OA that might affect chondrocyte apoptosis and senescence.ResultsmiR‐6779 was found to be significantly down‐regulated in OA. Seventy‐six of the predicted and miR‐6779 targeted genes and the OA‐associated disease genes overlapped, and these were enriched in cell proliferation, cell apoptosis, and cell cycle. miR‐6779 overexpression remarkably attenuated IL‐1β effects on chondrocytes by reducing MMP3 and MMP13 levels, promoting cell apoptosis, suppressing cell senescence, and increasing caspase‐3, caspase‐9 and reducing P16 and P21 levels. miR‐6779 targeted inhibition of X‐linked inhibitor of apoptosis protein (XIAP) expression. XIAP knockdown partially improved IL‐1β‐induced chondrocyte senescence and dysfunction. Lastly, when co‐transfected with a miR‐6779 agomir, the XIAP overexpression vector partially attenuated the effects of miR‐6779 overexpression on chondrocytes; miR‐6779 improved IL‐1β‐induced senescence and dysfunction in chondrocytes through targeting XIAP.ConclusionmiR‐6779 is down‐regulated, and XIAP is up‐regulated in OA cartilage and IL‐1β‐treated chondrocytes. miR‐6779 inhibits XIAP expression, thereby promoting senescent chondrocyte cell apoptosis and reducing chondrocyte senescence and ECM loss through XIAP.
Diplatinum Single‐Molecular Photocatalyst Capable of Driving Hydrogen Production from Water via Singlet‐to‐Triplet Transitions
Authors: Kunikubo Toma , Castañeda Raúl , Murugesu Muralee , Brusso Jaclyn L. , Yamauchi Kosei , Ozawa Hironobu , Sakai Ken 
Published: February 2025

AbstractSolar‐driven hydrogen production is regarded as one of the most ideal methods to achieve a sustainable society. In order to artificially establish efficient photosynthetic systems, efforts have been made to develop single‐molecular photocatalysts capable of serving both as a photosensitizer (PS) and a catalyst (Cat) in hydrogen evolution reaction (HER). Although examples of such hybrid molecular photocatalysts have been demonstrated in the literature, their solar energy conversion efficiencies still remain quite limited. Here we demonstrate that a new dinuclear platinum(II) complex Pt2(bpia)Cl3 (bpia=bis(2‐pyridylimidoyl)amido) serves as a single‐molecular photocatalyst for HER with its performance significantly higher than that of the PtCl(tpy)‐ and PtCl2(bpy)‐type photocatalysts developed in our group (tpy=2,2':6′,2''‐terpyridine, bpy=2,2′‐bipyridine). The outstanding feature is that Pt2(bpia)Cl3 can produce H2 even by irradiating the lower‐energy light above 500 nm, which is rationalized due to the direct population of triplet states via singlet‐to‐triplet transitions (i.e., S‐T transitions) accelerated by the diplatinum core. To the best of our knowledge, Pt2(bpia)Cl3 is the first example of a single‐molecular photocatalyst enabling hydrogen production from water via the S‐T transitions using lower‐energy light (>580 nm).
Total Synthesis of Discobahamin A and Putative Structure of Discobahamin B via an Isocyanide‐based Macrocyclization Reaction
Authors: Yang Baochao , Wang Qian , Zhu Jieping 
Published: February 2025

AbstractWe report in this paper the first total synthesis of discobahamin A, a 24‐membered macrocyclopeptide containing an α‐keto amide functional group. We assign the absolute configuration of 2‐hydroxy‐3‐methylpentanoic acid (Hmp), the side chain capping the N‐terminus of the macrocycle, as the (2S, 3S) stereoisomer. A novel macrocyclization strategy was developed, utilizing an intramolecular Passerini reaction between ω‐isocyano aldehyde and acetic acid. Notably, this macrocyclization proceeds via C(sp3)‐C(sp2) bond formation and de novo generation of an α‐keto amide functional group. Furthermore, we synthesized both the proposed structure of discobahamin B and its diastereomer. However, the spectroscopic data for these two compounds do not fully align with those reported for discobahamin B.
Eine authentische Al=Si‐Doppelbindung
Authors: Parvin Nasrina , Ankur  , Morgenstern Bernd , Scheschkewitz David 
Published: February 2025

AbstractAluminatasilene sind die schwer zu fassenden schwereren Gegenstücke der bekannten Borataalkene, bei denen die B=C‐Doppelbindung formal durch eine Al=Si‐Einheit ersetzt ist. Wir berichten über die Isolierung eines viergliedrigen anionischen AlSi3‐Rings mit einer echten Al=Si‐Doppelbindung, der durch die Reaktion von 2 Äquivalenten des Disilenids Tip2Si=SiTipLi mit H2AlCl (Tip=2,4,6‐Triisopropylphenyl) erhalten wird. Röntgenkristallographie, UV/Vis‐Spektroskopie und rechnerische Analysen bestätigen den Doppelbindungscharakter mit einer sehr kurzen Al−Si‐Bindung von 2.283(1) Å und einem hohen Wiberg‐Bindungsindex (WBI) von 1.31. Die intramolekulare C−H‐Aktivierung durch die Al=Si‐Bindung und die Reaktionen mit Schwefelquellen bestätigen eine typische Doppelbindungsreaktivität.
Regulating the Spatially Folded Arrangement of Donor and Acceptor Units To Achieve Efficient Orange‐Red Thermally Activated Delayed Fluorescence
Authors: Li Maoqiu , Hua Lei , Zhao Jinyang , Liu Yuchao , Yan Shouke , Ren Zhongjie 
Published: February 2025

AbstractAchieving efficient long‐wavelength organic light‐emitting diodes (OLEDs) remains a challenge due to the energy gap law, which leads to increased non‐radiative decay rates as the emission wavelength shifts to longer regions. Herein, a strategy of constructing folded three‐dimensional architectures is proposed to explore new orange‐red thermally activated delayed fluorescence (TADF) emitters with through‐space charge transfer characteristics. Innovatively, naphthalene is selected as a bridge to connect O‐bridged triphenylamine donor and planar dibenzo[a,c]phenazine acceptor respectively via simple Suzuki–Miyaura Coupling. In this way, a series of rigid orange‐red emitters with “U”‐shaped, folded “Z”‐shaped and “W”‐shaped configurations are elaborately constructed by modifying end groups, adjusting the numbers of naphthalene and donor, and regulating the linkage sites. The excited state natures and photophysical properties of the emitters can be effectively regulated and optimized by changing three‐dimensional architectures. Finally, the prepared emitter QX36 achieves a lower non‐radiative transition rate, a higher radiative rate and a higher photoluminescence quantum efficiency. Solution‐processed OLEDs based QX36 present the excellent electroluminescent performance with a maximum external quantum efficiency (EQE) of up to 32.3 % and EQE of 20.6 % at 1000 cd m−2, which are the leading values of solution‐processed orange‐red OLEDs. This work demonstrates the promising potential of folded TADF based naphthalene backbone as emitters for future efficient solution‐processed long‐wavelength OLEDs.
Self‐optimizing Cobalt Tungsten Oxide Electrocatalysts toward Enhanced Oxygen Evolution in Alkaline Media
Authors: Nickel Christean , Troglauer David Leander , Dallos Zsolt , Abid Dhouha , Sowa Kevin , Cichocka Magdalena Ola , Kolb Ute , Mashtakov Boris , Mohazzab Bahareh Feizi , Han Shikang , Prädel Leon , Ci Lijie , Li Deping , Lin Xiaohang , Hua Minghao , Liu Rongji , Gao Dandan 
Published: February 2025

AbstractSelf‐optimizing mixed metal oxides represent a novel class of electrocatalysts for the advanced oxygen evolution reaction (OER). Here, we report self‐assembled cobalt tungsten oxide nanostructures on a lab‐synthesized copper oxide substrate through a single‐step deposition approach. The resulting composite exhibits remarkable self‐optimization behavior, shown by significantly reduced overpotentials and enhanced current densities, accompanied with substantial increase in OER kinetics, electrocatalytically active surface area, surface wettability, and electrical conductivity. Under operating conditions, interfacial restructuring of the electrocatalyst reveals the in situ formation of oxidized cobalt species as the true active site. Complementary density functional theory (DFT) calculations further demonstrate the formation of *OOH intermediate as the rate‐determining step of OER, and highlight the adaptive binding of oxygen intermediates, which transitions from tungsten to cobalt site during OER process. Our study provides a fundamental understanding of the self‐optimization mechanism and advances the knowledge‐driven design of efficient water‐splitting electrocatalysts.
Enhanced Interfacial Electric Field of an S‐Scheme Heterojunction by an Ultrasonication‐Triggered Piezoelectric Effect for Sonocatalytic Therapy of Bacterial Infections
Authors: Wei Junwu , Zhang Guiyuan , Xie Shuang , Zhang Zhanlin , Gao Tianyu , Zhang Mengxue , Li Xiaohong 
Published: February 2025

AbstractSonodynamic therapy indicates advantages in combating antibiotics‐resistant bacteria and deep tissue infections, but challenges remain in the less efficient charge transfer and reactive oxygen species (ROS) generation of sonosensitizers. Herein, an effective bactericidal strategy is developed through enhancing the interfacial electric field (IEF) of S‐scheme heterojunctions by an ultrasonication‐triggered piezoelectric effect. Hollow barium titanate (hBT) nanoparticles (NPs) were prepared through template etching, followed by in situ assembly of tetrakis (4‐carboxyphenyl)porphyrin (TCPP) with Zn2+ to obtain hBT@ZnTCPP. Both experimental and theoretical evidences support the notion that an IEF is generared from ZnTCPP to hBT. Compared to metalloporphyrins with Fe3+, Mn3+, Cu2+ and Ni2+, the stronger reduction of ZnTCPP induced by elevation of the orbital energy level of porphyrins after Zn2+ coordination leads to formation of S‐scheme heterojunctions. The ultrasonication‐activated polarization field enhances IEF and boosts energy band bending of hBT@ZnTCPP to promote electron‐hole separations and ROS generations. Planktonic methicillin‐resistant Staphylococcus aureus and their derived biofilms are completely destroyed within 5 min under ultrasonication through up‐regulating genes of glucose catabolism and ion transportation and down‐regulating genes of ribosomal synthesis and transmembrane transporter. Thus, this study demonstrates molecular‐level modulation of energy levels for S‐scheme heterojunction formation to achieve efficient sonocatalytic therapy of bacterial infections.