bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surface Defects Control Bulk Carrier Densities in Polycrystalline Pb‐Halide Perovskites
Authors: Cahen David , Rakita Yevgeny , Egger David A. , Kahn Antoine 
Published: October 2024

AbstractThe (opto)electronic behavior of semiconductors depends on their (quasi‐)free electronic carrier densities. These are regulated by semiconductor doping, i.e., controlled “electronic contamination”. For metal halide perovskites (HaPs), the functional materials in several device types, which already challenge some of the understanding of semiconductor properties, this study shows that doping type, density and properties derived from these, are to a first approximation controlled via their surfaces. This effect, relevant to all semiconductors, and already found for some, is very evident for lead (Pb)‐HaPs because of their intrinsically low electrically active bulk and surface defect densities. Volume carrier densities for most polycrystalline Pb‐HaP films (<1 µm grain diameter) are below those resulting from even < 0.1% of surface sites being electrically active defects. This implies and is consistent with interfacial defects controlling HaP devices in multi‐layered structures with most of the action at the two HaP interfaces. Surface and interface passivation effects on bulk electrical properties are relevant to all semiconductors and are crucial for developing those used today. However, because bulk dopant introduction in HaPs at controlled ppm levels for electronic‐relevant carrier densities is so difficult, passivation effects are vastly more critical and dominate, to first approximation, their optoelectronic characteristics in devices.
A Synergistically Enhanced Triboelectric‐Electromagnetic Hybrid Generator Enabled by Multifunctional Amorphous Alloy for Highly Efficient Self‐Powered System
Authors: Gong Shaokun , Tang Benzhen , Liu Chengxu , Zhao Wei , Chen Jie , Yu Peng , Guo Hengyu 
Published: October 2024

AbstractTriboelectric‐electromagnetic hybrid generator (TEHG) has emerged as an effective technology for mechanical energy harvesting. However, the independent operation of triboelectric nanogenerator (TENG) and electromagnetic generator (EMG), along with tribo‐materials wear and magnetic field divergence, constrain the device's overall performance. To address these challenges, a synergistically enhanced TEHG (SE‐TEHG) is proposed based on the multifunctional amorphous alloy. Following detailed material analyses, Fe72Si8B20 is selected as the synergistic layer for its low surface roughness, high Vickers‐hardness, amorphous structure, and high magnetization. Compared to Al, this material not only boosts TENG's output current and current retention rate by 28.75% and 85.24%, but also improves EMG's output power by 51.05%. In constructing a self‐powered system with TEHG, a significant impedance discrepancy exists between the energy harvester (with matched impendence of 16 MΩ for TENG and 110 kΩ for EMG) and the application end. Without power management circuits, the demonstrated self‐powered variable impedance system achieves an energy utilization efficiency that is 2.98 times greater than the conventional constant impedance system. The integration of multifunctional materials to realize strong‐coupling hybrid generators, combined with the customization of variable impedance systems, set a milestone in efficient mechanical energy harvesting and utilization.
Improving the Photochemical Skeletal Enlargement of Pyridines to 1,2‐Diazepines with Isocyanates
Authors: Ghiazza Clément , Damond Aurélie , Marrot Jérôme , Moreau Xavier 
Published: October 2024

AbstractIn this work, we extend the one‐pot protocol to synthesize 1,2‐diazepines from commercially available and cheap starting materials. Capitalizing on isocyanate derivatives as activating agents, the photochemical skeletal enlargement occurs, while preserving key functional groups embedded in more than 30 substrates. We also demonstrated that isocyanates can be generated in situ exploiting the wealth of methods starting from bench stable resources. Compare to previous strategies, the use of these precursors prevents the presence of deleterious HCl traces in the system, thus enabling the synthesis of 1,2‐diazepines in high yields over up to 5 sequential steps.
From Synthesis to Energy Storage, The Microchemistry of MXene and MBene
Authors: Chen Jie , Zhang Wei , Chen Ruwei , Dai Yuhang , Zhang Jichao , Yang Hang , Zong Wei , Jiang Zhengjing , Zhong Yunpeng , Wang Jingyi , Zhang Xinyu , He Guanjie 
Published: October 2024

AbstractMXene and MBene, with diverse and adjustable surface and bulk structures, show many unique chemical properties and are applied in various energy storage technologies, and the latest developments for them are reviewed respectively. However, the current reports on the synthesis of the two materials and the application of related devices are still separate and limited to the macro details. In this review, the microscopic chemistry of synthesis strategies for MXene and MBene and the differences in synthesis strategies caused by the structure differences between them are elucidated. Later, the impact of synthesis strategies on their overall morphologies and subsequent material property differences are discussed, and key considerations in the field of energy storage are described. Next, it is elaborated on how the surface and bulk phases of MXene and MBene utilize these properties to participate in electrochemical reactions individually or synergistically. Unlike previous reviews, MXene and MBene are incorporated into a unified framework from a microscopic perspective for discussion, and the relationship of synthesis‐structure/properties‐function is elucidated. Finally, the “skipping strategy” and “joint devices” as the next‐generation design concepts of MXene in the synthesis and application fields, and the development template for MBene materials are proposed.
Mitigating Long Range Jahn‐Teller Ordering to Stabilize Mn Redox Reaction in Biphasic Layered Sodium Oxide
Authors: Li Shihao , Zhou Wei , Liu Fangyan , Guan Chaohong , Gao Xianggang , Zhang Yi , Jin Rui , Lai Yanqing , Zhang Zhian 
Published: October 2024

AbstractTo develop the next‐generation commercial oxide cathodes for sodium‐ion batteries, it is crucial to reduce the expensive Ni element content, and further regulate redox reaction of cheap transition metal elements such as Mn to elevate specific capacity. Nevertheless, the activation of Mn redox reaction (MRR) remains a challenge, and notably, MRR induces pronounced Jahn‐Teller effect, resulting in severe structural distortion and fast performance decay. Herein, activated by Na vacancies and weakened hybridization of O (2p)‐TM (3d‐t2g) orbital, a biphasic low‐Ni Mn‐based oxide P2/O3‐Na0.8Ni0.23Fe0.34Mn0.43O2 (P2/O3) exhibits reversible MRR, which performs the transition between Mn4+ and Mn3+ during charging and discharging. Due to the interlaced arrangement of P2‐type and O3‐type crystal domains in P2/O3, the long range Jahn‐Teller ordering is restricted to mitigate the cooperative distortion of MnO6 octahedron induced by MRR and the Jahn‐Teller effect is suppressed, ensuring sustained stable involvement of MRR in charge compensation. In addition, owing to the introduction of P2‐type phase, there is a significant reduction of the migration barrier for sodium ions and no obvious capacity decline after air exposure, leading to a marked enhancement in dynamic performance and air stability of P2/O3, respectively. Consequently, P2/O3 exhibits excellent electrochemical and processing performance.
The Operando Nature of Isobutene Adsorbed in Zeolite H−SSZ−13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy
Authors: Bocus Massimo , Vandenhaute Sander , Van Speybroeck Veronique 
Published: October 2024

AbstractUnraveling the nature of adsorbed olefins in zeolites is crucial to understand numerous zeolite‐catalyzed processes. A well‐grounded theoretical description critically depends on both an accurate determination of the potential energy surface (PES) and a reliable account of entropic effects at operating conditions. Herein, we propose a transfer learning approach to perform random phase approximation (RPA) quality enhanced sampling molecular dynamics simulations, thereby approaching chemical accuracy on both the determination and exploration of the PES. The proposed methodology is used to investigate isobutene adsorption in H−SSZ−13 as prototypical system to estimate the relative stability of physisorbed olefins, carbenium ions and surface alkoxide species (SAS) in Brønsted‐acidic zeolites. We show that the tert‐butyl carbenium ion formation is highly endothermic and no entropic stabilization is observed compared to the physisorbed complex within H−SSZ−13. Hence, its predicted concentration and lifetime are negligible, making a direct experimental observation unlikely. Yet, it remains a shallow minimum on the free energy surface over the whole considered temperature range (273–873 K), being therefore a short‐lived reaction intermediate rather than a transition state species.
Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates
Authors: Sheng Kai , Han Bao‐Liang , Wang Zhi , Gao Zhi‐Yong , Tung Chen‐Ho , Sun Di 
Published: October 2024

AbstractThe established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72, using two and three different anion templates, respectively. Ag57 features a gyroscope‐like monovalent cation with an Ag3 triangle core sandwiched by one [SiW9O34]10− and a triad of Cl− anion templates. By intentionally introducing the third anion template, SO42−, the structure is expanded to the unprecedented Ag72 (with 15 silver atoms epitaxially grown on top of Ag57) resembling a tumbler, inside of which two Ag3 layers are laminated by one [SiW9O34]10−, seven Cl− and one SO42− anion templates in parallel with respect to longitudinal orientation. It is noteworthy that Ag72 exhibits remarkable structural complexity and represents a pioneering achievement as the first silver cluster incorporating three distinct types of anion templates. In addition, Ag72 demonstrates a significant advantage over Ag57, particular in terms of applications such as luminescent thermometers and remote laser ignition. This work not only broadens the horizon for precise control of the silver cluster structures through the integration of multiple types of hetero‐anions but also lays a solid foundation for potential optical applications in the future.
Fluorescence Modulation through the Inverted Energy Gap Law in Triply N−B←N‐Containing Windmill‐Shaped Triazines
Authors: Feng Yi , Wang Liangxuan , Gao Hongcheng , Zhou Jiadong , Stolte Matthias , Qiu Honglin , Liu Linlin , Adebayo Victor , Boggio‐Pasqua Martial , Würthner Frank , Gierschner Johannes , Xie Zengqi 
Published: October 2024

AbstractA series of windmill‐shape heterocyclic molecules containing three N−B←N units, TBN and its derivatives, with quasi‐planar C3 symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum‐chemical calculations. Introducing peripheral phenyl‐ or thienyl‐groups (Ph‐TBN or Th‐TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials.
Localized High‐Concentration Electrolyte for All‐Carbon Rechargeable Dual‐Ion Batteries with Durable Interfacial Chemistry
Authors: Liu Rui , Xu Yan‐Song , Zhou Rui , Tan Shuang‐Jie , Li Yun‐Nuo , Jiang Si‐Jie , Xin Sen , Guo Yu‐Guo , Cao Fei‐Fei 
Published: October 2024

AbstractLithium‐based rechargeable dual‐ion batteries (DIBs) based on graphite anode‐cathode combinations have received much attention due to their high resource abundance and low cost. Currently, the practical realization of the batteries is hindered by easy oxidation of the electrolyte at the cathode interface, and solvent co‐intercalation at the anode‐electrolyte interface. Configuration of a “solvent‐in‐salt” electrolyte with a high concentration of Li salt is expected to stabilize the electrolyte chemistry versus both electrodes, yet inevitably reduces the mobility of the solvated working ions and increases the cost of the electrolyte. Herein, we propose to build a localized high‐concentration electrolyte by adding hydrofluoroether as the diluent to reduce the salt content while improving the solvation structure, allowing more anions to enter the inner solvation sheath. The new electrolyte helps to form uniform and thin interfaces, with elevated contents of inorganic fluorides, on both electrodes, which effectively suppress electrolyte oxidation at the cathode and optimize electrolyte‐electrode compatibility at the anode while facilitating charge transfer across the interface. Consequently, the DIBs with graphite as anode and cathode operate for 3000 cycles and retain a high‐capacity retention of 95.7 %, highlighting the importance of stable interfacial chemistry in boosting the electrochemical performance of DIBs.
Bowl‐Shaped Anthracene‐Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion
Authors: Wang Kaisheng , Ghosh Aninda , Shimizu Daiki , Takano Hideaki , Ishida Masatoshi , Kishi Ryohei , Shinokubo Hiroshi 
Published: October 2024

AbstractThe synthesis of bowl‐shaped antiaromatic molecules is challenging because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report the synthesis and properties of bowl‐shaped fused anthrylnorcorroles that exhibit near‐infrared (NIR) absorption reaching 1900 nm. The oxidation of meso‐anthryldibromodipyrrin provides fused anthryldibromodipyrrin, which was converted to the fused mono‐ and bisanthrylnorcorroles through Ni(0)‐mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single‐crystal X‐ray diffraction analyses revealed bowl‐shaped structures for the fused mono‐ and bisanthrylnorcorroles, which enables them to act as suitable receptors for C60 with bonding constants of 2.89×103 M−1 and 1.59×103 M−1, respectively. The formation of a 1 : 1 complex between the fused monoanthrylnorcorrole and C60 was confirmed by single‐crystal X‐ray diffraction analysis. The effective expansion of the π‐conjugation through the triple fusion of the norcorrole with the anthracene units substantially enhances the near‐infrared absorption bands, which endows these anthrylnorcorroles with effective photothermal conversion.
Soziale Kosten von Bauprojekten – systematische Literaturübersicht und Handlungsempfehlungen
Authors: Weissinger Marcel , Lieb Sarah , Jünger Hans Christian 
Published: October 2024

AbstractDie Weltbevölkerung nimmt derzeit noch zu. Der Bedarf an Wohnungen, Bildungs‐ und Betreuungseinrichtungen, Logistik und Infrastruktur in innerstädtischen Gebieten steigt. Die damit verbundenen Baumaßnahmen beeinträchtigen die Nachbarschaften, die Nutzungen des Quartiers sowie den städtischen Verkehr und verursachen gesellschaftliche Kosten für die umgebenden Strukturen (sog. soziale Kosten). Da der Fokus bei Investitionsentscheidungen von Bauherren aktuell jedoch überwiegend auf den Investitionskosten liegt, werden die sozialen Kosten nur selten in Bauprojekten berücksichtigt bzw. internalisiert. Sie sind folglich von der Gesellschaft zu tragen. International existieren bereits Untersuchungen zu den sozialen Kosten von Bauprojekten. Ein aktueller, ganzheitlicher und systematischer Überblick fehlt bislang. Indes gewinnen nachhaltige Maßnahmen in der Bauabwicklung, die auch die sozialen Kosten von Bauprojekten beeinflussen, durch internationale Regulierungen, wie bspw. die Sustainable Development Goals (SDG) und die EU‐Taxonomie (ESG‐Kriterien), sowie nationale Regulierungen, wie bspw. die CO2‐Bepreisung und das Klimaschutzgesetz in Deutschland, an Bedeutung. Um die Folgen dieser Vorgaben einer ökonomischen Bewertung zuführen zu können, wird im vorliegenden Beitrag eine systematische Literaturübersicht zu den sozialen Kosten durchgeführt. Dies wird mit dem Ziel verfolgt, den Einsatz verträglicherer Maßnahmen in der Bauabwicklung zu fördern und deren Mehrwerte für die Gesellschaft aufzuzeigen. Im Aufsatz liegt der Schwerpunkt auf Hochbauprojekten.
Conjugated polymers as photocatalysts for hydrogen therapy
Authors: Mi Feixue , Zhao Ningjing , Jin Lingyue , Zhang Ziyi , Wang Xinyu , Fang Xiaofeng , Li Wenting , Liu Zhao , Shu Peng , Zhang Xuanjun , Wu Changfeng 
Published: October 2024

AbstractHydrogen as a therapeutic agent has attracted a great deal of attention because of its superior therapeutic outcome on many diseases, including inflammatory injury, tumors, metabolic disorders, and neurological diseases. Photocatalytic hydrogen evolution has emerged as a promising strategy for hydrogen production and delivery. This review article presents the recent developments in the design and synthesis of conjugated polymer materials, including linear polymers and crosslinked conjugated materials, for photocatalytic hydrogen evolution. Particularly, we focus this review on the development of conjugated polymers as photocatalysts and the resulting hydrogen therapy in the fields of anti‐inflammatory, free radical scavenging, and cancer treatment. Finally, this article discusses the future research and perspective of conjugated polymer materials for hydrogen evolution and the potential clinical applications of hydrogen as a therapeutic agent.
ColMA‐based bioprinted 3D scaffold allowed to study tenogenic events in human tendon stem cells
Authors: Cortella Giacomo , Lamparelli Erwin Pavel , Ciardulli Maria Camilla , Lovecchio Joseph , Giordano Emanuele , Maffulli Nicola , Della Porta Giovanna 
Published: October 2024

AbstractThe advent of bioprinting has enabled the creation of precise three‐dimensional (3D) cell cultures suitable for biomimetic in vitro models. In this study, we developed a novel protocol for 3D printing methacrylated collagen (ColMa, or PhotoCol®) combined with tendon stem/progenitor cells (hTSPCs) derived from human tendon explants. Although pure ColMa has not previously been proposed as a printable hydrogel, this paper outlines a robust and highly reproducible pipeline for bioprinting this material. Indeed, we successfully fabricated a 3D bioengineered scaffold and cultured it for 21 days under perfusion conditions with medium supplemented with growth/differentiation factor‐5 (GDF‐5). This bioprinting pipeline and the culture conditions created an exceptionally favorable 3D environment, enabling the cells to proliferate, exhibit tenogenic behaviors, and produce a new collagen type I matrix, thereby remodeling the surrounding environment. Indeed, over the 21‐day culture period under perfusion condition, tenomodulin expression showed a significant upregulation on day 7, with a 2.3‐fold increase, compared to days 14 and 21. Collagen type I gene expression was upregulated nearly 10‐fold by day 14. This trend was further confirmed by western blot analysis, which revealed a statistically significant difference in tenomodulin expression between day 21 and both day 7 and day 14. For type I collagen, significant differences were observed between day 0 and day 21, as well as between day 0 and day 14, with a p‐value of 0.01. These results indicate a progressive over‐expression of type I collagen, reflecting cell differentiation towards a proper tenogenic phenotype. Cytokines, such as IL‐8 and IL‐6, levels peaked at 8566 and 7636 pg/mL, respectively, on day 7, before decreasing to 54 and 46 pg/mL by day 21. Overall, the data suggest that the novel ColMa bioprinting protocol effectively provided a conducive environment for the growth and proper differentiation of hTSPCs, showcasing its potential for studying cell behavior and tenogenic differentiation.
Single and Combinatorial Effects of Metformin and Thymoquinone in Diffuse Large B Cell Lymphoma Cells
Authors: Glamočlija Una , Mahmutović Lejla , Bilajac Esma , Šoljić Violeta , Vukojević Katarina , Sezer Abas , Suljagić Mirza 
Published: October 2024

AbstractDiffuse large B cell lymphoma (DLBCL) is classified into Germinal Center B‐cell (GCB) and activated B‐cell (ABC) subgroups originating from different stages of lymphoid differentiation. Cell of origin dictates the behavior and therapeutic response of DLBCL. This study aimed to evaluate single and combinatorial effects of metformin and thymoquinone (TQ) in two DLBCL cell lines belonging to GCB and ABC subtypes. Metformin and TQ caused dose‐dependent responses in both ABC and GCB DLBCL subtypes. Metformin had a greater impact on the ABC subtype while TQ demonstrated more pronounced effects on the GCB subtype. Synergistic effects were observed in the DHL4 (GCB subtype) but not in the HBL1 (ABC subtype) cell line. This is the first study to compare the effects of metformin and TQ in ABC versus GCB subtype of DLBCL. It brings valuable results that could be utilized in further research aimed at reshaping treatments for subtype‐specific lymphomas.
Plantago boissieri: Phytochemical Assessment, Antioxidant, Anti‐inflammatory and Wound Healing Potential
Authors: Amin Elham , Abouzeid Hala , Afifi Naglaa , Aboud Heba M. , Abd El‐Ghafar Omnia A. M. , Alabdulrahim Alya K. , Ahmed Hayam S. 
Published: October 2024

AbstractPlantago is a large genus under family Plantaginaceae. Several Plantago species were noted for potent antioxidant, anti‐inflammatory and wound healing activities. The current research investigated the potential bioactivities as well as the metabolic content of Plantago boisserei extract. Results highlighted the rich content of phenolics (450.93±7.4 mg GAE/g extract) and flavonoids (144.2±3.6 mg RE/g extract) in this species. HPLC analysis enabled the detection of 17 phenolic constituents among which ellagic acid was found in highest concentration (52.94 mg/g) followed by rutin (6.72 mg/g). Furthermore, P. boisserei extract exhibited a potent antioxidant activity evidenced by the IC50 values in ABTS and H2O2 assays (10.95 and 10.87 μg/mL, respectively) as well as in TAC assay (67.94 mg AAE/g). The anti‐microbial activities of the extract revealed a moderate activity against Staphylococcus aureus and Proteus vulgaris. In vitro testing of the anti‐inflammatory potential indicated a characteristic inhibition against COX‐1 and COX‐2 enzymes with IC50 62.8 and 14.23 μg/mL, respectively, compared to ibuprofen (IC50 8.07 and 6.58, respectively). Additionally, P. boisserei extract achieved a potent wound healing activity using in vivo rat model, this might be attributed to its high content of flavonoids together with other polyphenolic compounds that have a great free radical scavenging potential. In conclusion, P. boisserei is a promising candidate for more extensive phytochemical and biological exploration.