bluuebunny/crossref_metadata_2025_split huggingface dataset:
Leistung und Stabilität eines Korund‐Typ‐In2O3‐Katalysators für die Kohlendioxidhydrierung zu Methanol
Authors: Gili Albert , Brösigke Georg , Javed Mudassar , Dal Molin Emiliano , Isbrücker Philipp , Repke Jens‐Uwe , Hess Franziska , Gurlo Aleksander , Schomäcker Reinhard , Bekheet Maged F. 
Published: December 2024

AbstractDie Hydrierung von Kohlendioxid zu Methanol ist eine wichtige chemische Reaktion zur Speicherung von Energie in chemischen Bindungen, wobei Kohlendioxid als Energiesenke verwendet wird. Indiumoxid gehört zu den vielversprechendsten Kandidaten für den Ersatz des Kupfer‐ und Zinkoxid‐Katalysators, der industriell für Synthesegasgemische eingesetzt wird, aber aus Gründen der Instabilität weniger idonhaltig für Edukte mit Kohlendioxid ist. Das Polymorph des Indiumoxids und die Betriebsbedingungen müssen noch optimiert werden, um eine optimale und stabile Leistung zu erzielen. Indiumoxid‐Katalysatoren, die unterschiedliche rhomboedrische und kubische Phasenverhältnisse enthalten, wurden mit einem solvothermischen Verfahren synthetisiert und in einem idealerweise gemischten Gasphasenreaktor bewertet. Der reine rhomboedrische Katalysator zeigt die beste Leistung in Bezug auf die Ausbeute an Methanol, Selektivität und Stabilität. Die Phasenstabilität wurde mit Synchrotron in situ‐XRD und Rietveld‐Verfeinerung analysiert, um Aufschluss über die Stabilität der verschiedenen Phasen bei erweiterten Betriebsbedingungen zu geben. Abhängig von der Durchflussrate, der Temperatur und dem Wasserstoffpartialdruck kommt es zu einer Transformation des Kristallsystems von rhomboedrisch zu kubisch, bei dem schließlich inaktives metallisches Indium entsteht. Falls vorhanden, dient kubisches In2O3 als Ausgangszentrum, um den Übergang von kubisch zu rhomboedrisch zu induzieren, was die Leistung beeinträchtigt. Diese Ergebnisse ermöglichen ein sinnvolleres Katalysatordesign und eine Feinabstimmung der Betriebsbedingungen, um eine optimale und stabile Leistungfähigkeit zu gewährleisten.
How to Easily Depolymerize Polyurethane Foam Wastes by Superbase Catalysts in Ionic Liquids Below 100 °C
Authors: Villa Rocio , Salas Rebeca , Maciá María , Velasco Francisco , Altava Belén , García‐Verdugo Eduardo , Lozano Pedro 
Published: December 2024

AbstractThis study introduces a novel and sustainable approach using Ionic Liquids (ILs) as a non‐innocent solvent that enhances the performance of the basic catalysts to depolymerize polyurethane foam wastes (PUFWs) through hydrolysis, alcoholysis or aminolysis under mild conditions. The system is stable, fully recoverable, and reusable. Hydrolysis of PUFWs can occur in just 2 minutes at 95–98 °C, producing a white polyol that is easily separated and reused in new polyurethane synthesis. The method was successfully scaled up to depolymerize 200 g of PUFW per batch (1 kg overall depolymerization system). This scalability, combined with the medium‘s reusability without loss of effectiveness, highlights its strong potential for industrial applications.
Topotactic Transformation in Fe3O4 Induces Spontaneous Growth of Compositionally Diverse Nanostructures
Authors: Muhammad Faheem , Chen Xiwen , Sun Qi , Wang Yuting , Mo Dongze , Li Yuyang , Miao Leiying , Wei Hui 
Published: December 2024

AbstractTopotactic transformation is an emerging strategy for synthesizing materials with exotic functional properties. In this report, instead of producing new crystals with related structures, we exploited the topotactic transformation phenomenon to spontaneously produce compositionally diverse nanostructures on the transforming substrate. The surface of magnetite nanoparticles (Fe3O4 NPs) is topotactically transformed into maghemite (γ‐Fe2O3). Benefiting from such oxidation susceptibility of ultrasmall Fe3O4 NPs, we achieved spontaneous growth of metals (Ag, Au, Pt, and Pd), a non‐metal (Se), and a metal oxide (MnO2) based nanostructures onto the surface of Fe3O4. No spontaneous growth of nanostructures was observed when the oxidized Fe3O4 NPs were tested, likely due to the loss of the Fe2+‐associated mobile electrons. The obtained nanostructures displayed appreciable antioxidant activities, which we utilized to effectively treat inflammation in the intestines. It is anticipated that this synthetic route, based on topotactic transformation, represents a significant advancement in synthesizing various chemically diverse hetero‐nanostructures.
Visible‐Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis of Highly Functionalized Xanthenes with Antitumor Activity
Authors: Lin Shi‐Lin , Zhao Fen , Wei Fen , Shi Ying‐Tong , Wen Jing‐Kai , Yang Chao , Zhang Hao‐Shuo , Li Chuang‐Chuang , Liu Chang , Ye Wen‐Cai , Cheng Min‐Jing , Wang Lei 
Published: December 2024

AbstractHighly functionalized xanthenes possess an impressive range of bioactivities and daunting synthetic challenge due to their unique ring systems and stereocenters. Here, we report an unprecedented ketyl radicals‐induced skeletal rearrangement reaction of spirodihydrobenzofurans, enabled by zero‐valent iron as reducing agents via photoredox catalysis, facilitating the facile preparation of various highly functionalized xanthenes. The features of this protocol include high chemo‐ and regioselectivity, exceptionally mild conditions, a broad substrate scope, scalability to gram‐scale quantities, and consistent delivery of good to excellent yields. Mechanistic studies rationalize the function of this zero‐valent iron‐based reactivity in radical generation. Notably, this reaction was applied to the first asymmetric total synthesis of the complex polycyclic xanthene ent‐myrtucomvalones E−F. Moreover, this work led to the discovery of an agent with highly effective antiosteosarcoma activity in vitro and in vivo, potentially paving the way for the development of new xanthene‐based candidates for osteosarcoma treatment.
Diverse Synthesis of Arene‐Fused [n.1.1]‐Bridged Molecules via Catalytic Cycloaddition and Rearrangement Reactions
Authors: Yu Tao , Zhao Xue , Nie Zaicheng , Qin Lulu , Ding Zhengwei , Xu Liang , Li Pengfei 
Published: December 2024

AbstractAlthough great advancement has been made in synthesis of 3D bridged bicyclic[n.1.1]‐bioisosteres, facile construction of 2D/3D merged molecules incorporating bridged rings, as novel chemical space in drug discovery, remains a significant challenge. Herein a collective, selective, and diversity‐oriented approach for up to 6 types of 2D/3D polycyclic scaffolds featuring bicyclo[n.1.1] substructure is reported. A boronyl radical‐catalyzed [2σ+2π] cycloaddition between bicyclo[1.1.0]butanes and ortho‐quinone methides afforded spirocyclic compounds containing a bicyclo[2.1.1]hexanes unit, which were used as intermediates for synthesis of three types of 2D/3D scaffolds via judiciously controlled Lewis acid‐catalyzed rearrangements. The reaction and rearrangement of para‐quinone methides worked analogously and provided another two polycyclic scaffolds.
Rapid N2O Formation from N2 on Water Droplet Surfaces
Authors: Jiang Qi , Xia Deming , Li Xiaofan , Zhang Hong , Yin Rujing , Xie Huaijun , Xie Hong‐bin , Jiang Jie , Chen Jingwen , Francisco Joseph S. 
Published: December 2024

AbstractNitrogen (N2) has long been considered as stable atmospheric reservoir for N element and has a persistence time of hundreds of years. This study reveals that oxygen (O2) at typical tropospheric concentrations can rapidly activate N2, leading to substantial production of nitrous oxide (N2O), the third most impactful greenhouse gas, at rates approaching 2.83±0.41 ppmv hour−1 catalyzed by ubiquitous water droplets in experimental systems. Notably, ozone (O3), typically consumed by N2O in the stratosphere, can further accelerate N2O formation. In contrast, the produced N2O concentration is below detection limits in the absence of O2/O3 or water droplets. A novel reduction‐then‐oxidation (RTO) mechanism was proposed to account for the rapid formation of N2O on the water droplet surfaces facilitated by the cooperation of water droplets and O2/O3. Further extrapolation indicates that the RTO pathway contributes several Tg N N2O annually, far exceeding the most known sources of N2O. These findings have broad implications for tracing atmospheric N2O sources, enhancing understanding of climate‐O2/O3 interactions, and paving avenues for developing new methodologies for N2O synthesis.
A High‐Entropy Engineering on Sustainable Anionic Redox Mn‐Based Cathode with Retardant Stress for High‐Rate Sodium‐Ion Batteries
Authors: Liu Shiqi , Liu Fangzheng , Zhao Shu , Zhuo Zengqing , Xiao Dongdong , Cui Zhongyi , Wang Yulong , Wang Boya , Wu Tianhao , Li Yuming , Liang Lisi , Huang Houbing , Yang Wanli , Yu Haijun 
Published: December 2024

AbstractManganese‐based (Mn‐based) layered oxides have emerged as competitive cathode materials for sodium‐ion batteries (SIBs), primarily due to their high energy density, cost‐effectiveness, and potential for mass production. However, these materials often suffer from irreversible oxygen redox reactions, significant phase transitions, and microcrack formation, which lead to considerable internal stress and degradation of electrochemical performance. This study introduces a high‐entropy engineering strategy for P2‐type Mn‐based layered oxide cathodes (HE‐NMCO), wherein a multi‐ingredient cocktail effect strengthens the lattice framework by modulating the local environmental chemistry. This innovative approach fosters sustainable reversible oxygen activity, mitigates stress concentrations at grain boundaries, and accelerates Na+ transport kinetics. The resulting robust lattice framework with optimized elemental interactions significantly improves structural integrity and reduces the formation of intragranular fractures. Consequently, HE‐NMCO demonstrates remarkable cycling stability, retaining 93.5 % capacity after 100 deep (de)sodiation cycles, alongside an enhanced rate capability of 134.1 mAh g−1 at 5 C. Notably, comparative studies through multimodal characterization techniques highlight HE‐NMCO′s superior reversibility in oxygen anion redox (OAR) reactions over extensive cycling, contrasting sharply with conventional NMCO cathode. This work elucidates the potential for advancing high energy and power density Mn‐based cathodes for SIBs through local species diversity.
Synergistic Pathways in PLA Breakdown and PTMC Formation: A One‐Pot Eutectic‐Driven Recycling Mechanism
Authors: Moins Sébastien , Coulembier Olivier 
Published: December 2024

AbstractThis study introduces a novel one‐pot strategy for the chemical valorization of poly(lactic acid) (PLA), coupling its base‐catalyzed depolymerization with the ring‐opening polymerization (ROP) of trimethylene carbonate (TMC). The process exploits an eutectic mixture of lactide (LA) and TMC, which lowers the thermal input required for PLA degradation. Using potassium aryloxide (KOArtBu) as a bifunctional catalyst, the PLA is first quickly hydrolyzed into oligomers or lactic acid, which subsequently initiate the slower polymerization of TMC. Notably, this transformation operates in the presence of residual water, eliminating the need for tedious drying steps. The method achieves selective PLA breakdown conversion and produces (oligo)lactic acid end‐capped poly(trimethylene carbonate) (PTMC) with tunable molar mass, depending on water content.
Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage
Authors: Bhadouria Ashutosh , Heil Joseph N. , Parab Durvesh E. , Greeley Jeffrey P. , Tackett Brian M. 
Published: December 2024

AbstractC−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C3H2* was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.
Hour‐Long Afterglow in Flexible Polymeric Materials through the Introduction of Electron Donor/Acceptor Exciplexes
Authors: Shi Jiaju , Zhang Peng , Gao Haiyang , Zhu Fangming , Liang Guodong 
Published: December 2024

AbstractThe development of organic afterglow materials has garnered significant attention due to their diverse applications in smart devices, optoelectronics, and bioimaging. However, polymeric afterglow materials often suffer from short emission lifetimes, typically ranging from milliseconds to seconds, posing a significant challenge for achieving hour‐long afterglow (HLA) polymers. This study presents the successful fabrication of transparent HLA polymers by introducing electron donor/acceptor exciplexes. Employing aromatic polyesters as the polymer electron acceptor and charge reservoirs, the resulting HLA polymers exhibited a remarkable green afterglow that persisted for 12 hours under ambient conditions, representing the longest duration achieved for polymeric afterglow materials to date. Intriguingly, these HLA polymers could be activated solely by sunlight, maintaining a green afterglow for over 6 hours at room temperature in air, which outperformed all previously reported afterglow polymers. The doped polymers exhibited superior flexibility and transparency, making them ideal candidates for flexible display applications. Furthermore, successfully spinning these doped polymers into fibers while retaining their HLA properties opens up exciting possibilities for their use in wearable smart devices.
Stimuli‐Responsive DNA Nanomachines for Intracellular Targeted Electrochemiluminescence Imaging in Single Cells
Authors: Li Binxiao , Lu Yanwei , Huang Xuedong , Sojic Neso , Jiang Dechen , Liu Baohong 
Published: December 2024

AbstractElectrochemiluminescence (ECL) microscopy has emerged as a powerful technique for single‐cell imaging owing to its unparalleled background‐free imaging advantages. However, controlled intracellular ECL imaging remains challenging. Here, we developed a stimuli‐responsive self‐assembled DNA nanomachine that enables the ECL imaging of intracellular target biomolecules in single cells. The ECL nanoprobe consists of an ECL nanoemitter constructed from Ru(bpy)32+‐doped metal–organic framework as the nanoreactor core, with a DNA polymer hydrogel (DNAgel) shell acting as the stimuli‐gated layer. The outer functionalized DNAgel of the ECL nanoprobe was specifically designed to block ECL generation and to dissociate by ATP molecules, thereby enabling selective recovery of ECL emission capability. Such an engineered stimuli‐responsive nanomachine successfully achieved the targeted ECL imaging of intracellular ATP distribution with spatial resolution. In addition, ECL imaging of various intracellular biomolecules should be generalizable by simply changing the switching DNA sequence of the probe. Our research provided a reliable strategy for ECL microscopy within cells, which will broaden the application of ECL in single‐cell and single‐molecule profiling.
Flexible Fiber Sensors for Real‐Time Monitoring of Redox Signaling Molecules in Exercise‐Mimicking Engineered Skeletal Muscle
Authors: Li Jia‐Xin , Fan Wen‐Ting , Sun Meng‐Yuan , Zhao Yi , Lu Yi‐Fei , Yang Yan‐Bing , Huang Wei‐Hua , Liu Yan‐Ling 
Published: December 2024

AbstractReal‐time monitoring of reactive oxygen and nitrogen species (RONS) in skeletal muscle provides crucial insights into the cause‐and‐effect relationships between physical activity and health benefits. However, the dynamic production of exercise‐induced RONS remains poorly explored, due to the lack of sensing tools that can conform to soft skeletal muscle while monitor RONS release during exercise. Here we introduce dual flexible sensors via twisting carbon nanotubes into helical bundles of fibers and subsequent assembling electrochemical sensing components. These flexible sensors exhibit low bending stiffness, excellent H2O2 and NO sensing abilities, outstanding biocompatibility and compliance with engineered skeletal muscle tissue. This allows real‐time and simultaneous monitoring of H2O2 and NO release from engineered skeletal muscle in response to different exercise‐mimicking stretches, which reveals that warm‐up activities before high‐intensity exercise may enhance adaptive responses by down‐regulating H2O2 and up‐regulating NO production. The proposed sensing strategy demonstrates great versatility in monitoring multiple biomarkers of soft tissue and organs.
Isomerization‐Controlled Aggregation in Photoactive Layer: An Additive Strategy for Organic Solar Cells with Over 19.5 % Efficiency
Authors: Xia Zihao , Gao Chuanlin , Xie Zhixiang , Wu Miaoxuan , Chen Hansheng , Li Tongzi , Zhou Jiang , Cai Ting , Hu Huawei , Shuai Jing , Xie Chen , Zhang Guangye , Chen Wenduo , Liu Shenghua 
Published: December 2024

AbstractMorphology control of the photoactive layer is crucial for achieving high‐performance organic solar cells (OSCs), yet it remains a significant challenge in this field. One effective approach is the additive strategy, which fine‐tunes the morphology of the photoactive layer. However, the underlying mechanisms governing the impact of different types of additives from liquid, solid, to volatile solid, on the bulk heterojunction morphology and device performance are not fully understood. Herein, we present an aggregation regulation strategy for acceptor molecules by incorporating three novel isomeric additives: 4‐bromo‐1,2‐dichlorobenzene (LCB), 1‐bromo‐2,4‐dichlorobenzene (SCB), and 2‐bromo‐1,4‐dichlorobenzene (VCB) into the blend active layer. This approach optimizes the bulk heterojunction morphology and enhances the photovoltaic performance of OSCs. Our results reveal that these additives induce stepwise regulation of acceptor molecule aggregation during film formation. The liquid additive LCB primarily extends solvent evaporation time, effectively preventing excessive aggregation, while the solid additive SCB significantly shortens the aggregation period during the film evolution, resulting in the most compact molecular π–π stacking. Furthermore, the volatile solid additive VCB fine‐tunes the intermolecular interactions and crystallization within the active layer, promoting optimal molecular self‐assembly and aggregation for ideal molecular stacking. Consequently, the power conversion efficiencies of 19.33 % and 19.51 % were achieved for the VCB‐processed D18 : L8‐BO‐ and PM6 : L8‐BO‐based OSCs, respectively, outperforming the LCB‐processed and SCB‐processed devices.
Through Space π‐Electrons Communication in [2,2]‐Paracyclophanes: Unprecendented Stabilization of Radicals
Authors: Fauvel Eléa , Moussounda Moussounda Koumba Tataye , El Kadiry Firas , Maria Sébastien , Rollet Marion , Maresca Marc , Siri Didier , Clément Jean‐Louis , Gigmes Didier , Nechab Malek 
Published: December 2024

AbstractEfforts to understand radical stability have led to considerable progress in radical chemistry. In this article, we investigated a novel approach to enhancing the radical stability of carbon‐centered radicals through space electron delocalization within [2,2]‐paracyclophanes. Alkoxyamines possessing a paracyclophane scaffold exploit face‐to‐face π‐π‐interactions between the aromatic rings to effectively lower bond dissociation energy (BDE) for NO−C bond homolysis. Electron spin resonance (ESR) experiments and computational modeling have confirmed a better stability compared to the analogues without the paracyclophane core. Theoretical analyses further elucidate the role of through‐space electron communication in enhancing radical stability. This study highlights promising applications in fields such as organic synthesis, material science, and drug design. By achieving a low BDE for homolysis, the alkoxyamines efficiently release radicals, enabling successful application in nitroxide‐mediated polymerization (NMP) of styrene, which provides high control over polymer architecture. Additionally, preliminary anti‐proliferative assays reveal that the alkoxyamines exhibit promising anti‐cancer activities against lung, breast, and prostate cells, which is correlated to their ability to release radicals upon homolysis.
Mit Hybriden Enzym‐Elektrokatalysator‐Kaskaden Modifizierte Gasdiffusionselektroden für die Methanolerzeugung aus Kohlendioxid
Authors: Wang Panpan , Wang Xin , Chandra Shubhadeep , Lielpetere Anna , Quast Thomas , Conzuelo Felipe , Schuhmann Wolfgang 
Published: December 2024

AbstractWir schlagen eine hybride elektrokatalytisch‐bioelektrokatalytische Reaktionskaskade vor, die auf einer Gasdiffusionselektrode zur CO2‐Reduktion unter selektiver Bildung von Methanol integriert ist. Ag‐Bi2O3 reduziert gasförmiges CO2 bei neutralem pH‐Wert selektiv zu Formiat. Eine nachfolgende enzymatische Kaskade aus Formaldehyd‐Dehydrogenase und Alkohol‐Dehydrogenase, die beide von Nikotinamid‐Adenin‐Dinukleotid (NADH) abhängig sind, reduziert Formiat weiter sequentiell zu Formaldehyd und Methanol. Der enzymatisch oxidierte Redoxkofaktor NAD+ wird durch das Enzym Diaphorase regeneriert, das elektrochemisch an die Elektrode gekoppelt ist, indem es in ein Redoxpolymer auf Cobaltocen‐Basis eingebettet ist. Die Methanolbildung wird mithilfe eines hochselektiven Biosensors nachgewiesen, der auf Alkoholoxidase in Kombination mit Meerrettichperoxidase basiert, die in ein speziell angepasstes Redoxpolymer integriert sind. Die vorgeschlagene hybride elektrokatalytisch‐bioelektrokatalytische Kaskade ist ein Beispiel für eine allgemeine Strategie zur Verbesserung der Selektivität elektrokatalytischer Reaktionen und/oder zum Ersatz bioelektrochemisch anspruchsvoller Schritte wie der Synthese von Formiat aus CO2 unter Verwendung sauerstoffempfindlicher Formiatdehydrogenasen durch robustere anorganische Elektrokatalysatoren.