bluuebunny/crossref_metadata_2025_split huggingface dataset:
Skeletal Editing of Aromatic N‐Heterocycles via Hydroborative Cleavage of C−N Bonds—Scope, Mechanism, and Property
Authors: Ren Chunping , Han Bo , Guo Hui , Yang Wendi , Xia Chungu , Jin Xu‐Hui , Wang Fang , Wu Lipeng 
Published: August 2024

AbstractSkeletal editing of the core structure of heterocycles offers new opportunities for chemical construction and is a promising yet challenging research topic that has recently gained increasing interest. However, several limitations of the reported systems remain to be addressed. For example, the reagents employed are generally in high‐energy, such as chlorocarbene precursors, nitrene species, and metal carbenes, which are also associated with low atomic efficiencies. Thus, the development of simple systems for the skeletal editing of heterocycles is still desired. Herein, a straightforward and facile BH3‐mediated skeletal editing of readily available indoles, benzimidazoles, and several other aromatic heterocycles is reported. Structurally diverse products were readily obtained, including tetrahydrobenzo azaborinines, diazaboroles, O‐anilinophenylethyl alcohols, benzene‐1,2‐diamines, and more. Density functional theory (DFT) calculations and natural bond orbital (NBO) analysis revealed a BH3‐induced C−N bond cleavage reaction pathway. An exciting and counterintuitive indole hydroboration phenomenon of −BH2 shift from C3‐position to C2‐position was disclosed. Moreover, the photophysical properties of the synthesized diazaboroles were studied, and an interestingly and pronounced aggregation‐induced emission (AIE) behavior was disclosed.
Celebrating Ten Years of Covalent Organic Frameworks for Solar Energy Conversion: Past, Present and Future
Authors: Rodríguez‐Camargo Andrés , Endo Kenichi , Lotsch Bettina V. 
Published: August 2024

AbstractAccelerated anthropogenic emission of greenhouse gases due to increasing energy demands has created a negative impact on our planet. Therefore, the replacement of fossil by renewable energy resources has become of paramount interest, both societally and scientifically. It is within this setting that organic photocatalysts have emerged as a new generation of earth‐abundant catalysts for the conversion of solar radiation into chemical energy. In 2014, the first example of a covalent organic framework (COF) photocatalyst for the hydrogen evolution reaction was reported by our group, which has not only marked the beginning of COF photocatalysis for solar fuel production but also helped to accelerate research into “soft photocatalysis” based on porous polymers in general. In the last decade, significant progress has been made toward developing COFs as robust, molecularly precise platforms emulating artificial photosynthesis. This mini‐review commemorates the 10th anniversary of COF photocatalysis and gives a brief historical overview of the milestones in the field since its inception in 2014. We review milestones in the development of COFs for solar fuel production and related photocatalytic transformations, including hydrogen evolution, oxygen evolution, overall water splitting, CO2 reduction, N2 fixation, oxygen reduction, and alcohol oxidation. We discuss lessons learned for the design of structure‐property‐function relationships in COF photocatalysts, and future perspectives and challenges for the field of “soft photocatalysis” are given.
Boosting Reactive Oxygen Species Generation via Contact‐Electro‐Catalysis with FeIII‐Initiated Self‐cycled Fenton System
Authors: Li Weixin , Tu Jialuo , Sun Jikai , Zhang Yuanbao , Fang Jiale , Wang Mingda , Liu Xiangyu , Tian Zhong‐Qun , Ru Fan Feng 
Published: August 2024

AbstractContact Electro‐Catalysis (CEC) using commercial dielectric materials in contact‐separation cycles with water can trigger interfacial electron transfer and induce the generation of reactive oxygen species (ROS). However, the inherent hydrophobicity of commercial dielectric materials limits the effective reaction sites, and the generated ROS inevitably undergo self‐combination to form hydrogen peroxide (H2O2). In typical CEC systems, H2O2 does not further decompose into ROS, leading to suboptimal reaction rates. Addressing the generation and activation of H2O2 is therefore crucial for advancing CEC. Here, we synthesized a catalyst by loading the dielectric material polytetrafluoroethylene (PTFE) onto ZSM‐5 (PTFE/ZSM‐5, PZ for short), achieving uniform dispersion of the catalyst in water for the first time. The introduction of an FeIII‐initiated self‐cycling Fenton system (SF‐CEC), with the synergistic effects of O2 activation and FeIII‐activated H2O2, further enhanced ROS generation. In the FeIII‐initiated SF‐CEC system, the synergistic effects of ROS and protonated azo dyes enabled nearly 99 % degradation of azo dyes within 10 minutes, a sixfold improvement compared to the CEC system. This represents the fastest degradation rate of methyl orange dye induced by ultrasound to date. Without extra oxidants, this system enabled stable dissolution of precious metals in weakly acidic solutions at room temperature, achieving 80 % gold dissolution within 2 hours, 2.5 times faster than similar CEC systems. This study also corrects the unfavorable perception of CEC applications under acidic conditions, providing new insights for the fields of dye degradation and precious metal recovery.
Tricyanomethane or Dicyanoketenimine—Silylation makes the Difference
Authors: Surkau Jonas , Bresien Jonas , Michalik Dirk , Schulz Axel 
Published: August 2024

AbstractPseudohalides such as tricyanomethanide, [C(CN)3]−, are well known in chemistry, biochemistry and industrial chemistry. The protonated species HC(CN)3, a classic hydrogen pseudohalide Brønsted acid, is a very strong acid with a pKa value of −5. However, HC(CN)3 is difficult to handle as it tends to decompose rapidly or, more precisely, to oligo‐ and polymerize. Therefore, silylated pseudohalide compounds with the [Me3Si]+ as the “big organometallic proton” have become interesting, exhibiting similar chemical properties but better kinetic protection. Here, the stepwise silylation of the pseudohalide anion [C(CN)3]− is reported, forming the heavier homologue of HC(CN)3, namely [Me3Si][C(CN)3], and in presence of two additional [Me3Si]+ cations even the dicationic species [(Me3Si−NC)3C]2+ as stable [B(C6F5)4]− salt. Surprisingly, in contrast to the protonated species HC(CN)3, in which the proton is bound to the central carbon atom of [C(CN)3]−, silylation of the [C(CN)3]− anion occurs at one of the three terminal nitrogen atoms, thus forming the long‐sought dicyanoketenimine [Me3Si−NC−C(CN)2]. All further silylation steps take place exclusively on the terminal N atoms of the three CN groups and not on the central carbon atom, until the intriguing, highly symmetrical dication, [(Me3Si−NC)3C]2+, is finally generated. The experimental data are supported by quantum chemical calculations in terms of thermodynamics and chemical bonding.
Time‐Encoded Information Encryption with pH Clock Guided Broad‐Spectrum Emission by Dynamic Assemblies
Authors: Das Priyam , Das Tanushree , Koley Suprotim , Kumar Baroi Malay , Das Saurav , Mohanty Jyotirmayee , Das Debapratim 
Published: August 2024

AbstractWith growing threats from counterfeiting‐based security breaches, multi‐level and specific stimuli‐responsive anti‐counterfeiting devices and message encryption methods have attracted immense research interest. Fluorescence‐based encryption from aggregation‐induced emission (AIE)‐based materials solves the problems to a considerable extent. However, the development of smarter patterns with hierarchical security levels alongside dynamic display is still challenging. To screen out this complication, we bring forward a pH‐switchable fluorescent assembly of an AIEgen and an aliphatic acid. We later temporally direct the molecular assembly with the aid of a chemical trigger‐regulated pH clock, generating a transitory multicolor emission, including transient white light generation. The pH‐dependent emissions were further implemented in constructing smart multi‐input fluorescent chemical AND gates. Subsequently, we integrate the time‐gated emissive system to develop an advanced multi‐dimensionally secure data encryption strategy. This novel approach enhances anti‐counterfeiting measures by introducing an additional layer of security based on temporal characteristics.
The chemical crosslinking effect of polybenzimidazole/polyvinyl alcohol blend membranes for proton exchange membrane fuel cells: An experimental study
Authors: Çalı Aygün , Ar İrfan 
Published: August 2024

AbstractIn this survey, the different weight ratios of polybenzimidazole (PBI)/polyvinyl alcohol (PVA) blend polymer membranes were produced using the solution‐casting method. The crosslinking agents of phosphoric acid (PA) and glutaraldehyde (GA) were studied separately to prevent the PVA water solubility in the PBI/PVA blend membrane structure. The GA crosslinking (24 h) successfully prevented membrane solubility, reducing it to below 1%. The chemically crosslinked blend membrane (Cr‐PBI/PVA‐9:1) has the highest proton conductivity result which is 0.209 S cm−1 at 80°C and it has excellent oxidative stability since the membrane only lost 4% of its weight in a Fenton agent after 96 h. The Cr‐PBI/PVA‐9:1 also has higher proton conductivity than the commercial PBI membrane (0.122 S cm−1 at 80°C). The glass transition temperature of the synthesized Cr‐PBI/PVA‐9:1 blend membrane is greater than the synthesized PBI membrane (390°C). The current density and power density measured at 0.6 V for the synthesized Cr‐PBI/PVA‐9:1 membrane were found to be 504 mA cm−2and 251 mW cm−2. This work sheds light on the potential use of PVA in PEMFC applications by mixing PVA with a high‐temperature polymer like PBI and crosslinking the membrane with a prepared GA crosslinking agent.
Development of shape memory epoxy resin/polyethylene glycol film based on molecular dynamics simulation and performance investigation
Authors: Hu Baoji , Zhai Manman , Shen Jiayi , Li Mengying , Shen Saibin , Liu Jianhong , Zhao Ningbo , Yang Shichang , Shao Weili , Zhang Qiaoling 
Published: August 2024

AbstractBased on the molecular dynamics (MD) simulation of glass transition temperature (Tg) and hydrogen bonding in the composite system of epoxy resin (Ep) and polyethylene glycol (PEG), this work developed shape memory Ep/PEG (EpP) films with controllable thermal response, recycling and reprocessing functions using melt dispersion and polymerizing‐pressing processes. EpP films with different PEG contents exhibit excellent shape memory performance, among which the shape recovery rate of EpP‐5 film can reach 92.7%, which can recover from complex structures to the initial shape. The PEG in the composite system can effectively regulate the thermal and mechanical properties of EpP, especially increasing the strain at break and reducing the Tg. Compared with EpP‐0 film. The Tg of EpP‐15 film increased by 40°C and the strain at break increased by 18.56%. Furthermore, compared with the EpP‐0 film, the recycling‐reprocessing temperature of EpP‐15 film has been reduced by 75°C. In summary, based on MD simulation, shape memory EpP films with controllable thermal response, recycling, and reprocessing functions have been successfully developed, and have shown considerable application prospects in the field of intelligent materials.
Natural light‐triggered microcapsules for non‐contact and autonomous healing of surface damages on insulating materials
Authors: Zhang Ying , Liu Qichang , Wang Mingwei , Niu Chaolu , Liu Zhe , Fang Zheng , Tang Wenxu , Chen Qiulin , Sun Potao , Sima Wenxia 
Published: August 2024

AbstractIn the process of curing or service, epoxy resin is prone to crack damage due to complex stress, resulting in material performance degradation and other catastrophic accidents. Self‐healing microcapsules offer an effective strategy to address the aforementioned issues and enhance the long‐term durability of materials. However, traditional microcapsules face challenges in achieving non‐contact repair, as the healing agent requires high temperature or other extreme conditions to achieve curing, which necessitates the artificial provision of these conditions. Moreover, such extreme conditions may accelerate equipment aging or negatively impact the matrix material. To address these issues, this paper reports a photosensitive microcapsule that can achieve healing by natural light for non‐contact self‐healing of insulating composites. In particular, SiO2 nanoparticles are incorporated into the shell of the microcapsules to construct a UV shielding layer, effectively preventing premature curing and failure of the untriggered microcapsules. Experimental results indicate that the proposed photosensitive microcapsule@SiO2 exhibits excellent thermal stability, remaining intact at temperatures up to 200°C. With a healing agent content of approximately 77.5%, the photosensitive microcapsule@SiO2 ensures effective repair. Furthermore, when cross‐linked with epoxy resin, it has minimal negative impact on the epoxy matrix, with a slight improvement in mechanical properties. The composites demonstrate outstanding self‐healing performance in response to mechanical scratch damage. Without the need for any artificial stimuli, the healing process can be easily activated by natural light, facilitating intelligent, contactless, and autonomous self‐healing.
A comprehensive analysis of photovoltaic panel integrated thermoelectric cooling system for enhanced power generation
Authors: Chandel Rahul , Chandel Shyam Singh , Prasad Deo , Dwivedi Ram Prakash 
Published: August 2024

AbstractThe integrated photovoltaic‐thermoelectric cooling systems (PV‐TECS) can be used to enhance the performance and life expectancy of commercial PV power plants for sustainable power generation. The objective of the study is to assess the efficacy of PV‐TECS to address these concerns. In this study, computational fluid dynamics/finite element method analysis and experimental investigation of photovoltaic micro‐modules (PVMM‐2) with a thermoelectric cooling system and a reference system without it (PVMM‐1), is carried out under real outdoor conditions. The logged data and infrared thermal imaging analysis results show that thermoelectric cooling is very effective in maintaining a consistent PV back temperature difference of 18.24°C between PVMM‐2 and the reference system, even reaching subzero temperature when the reference module operates close to 60°C. The simulated results are found to be in close agreement with the experimental results (R2 values of 0.83 and 0.94) which allows accurate prediction of system performance under actual solar loading conditions. Further analysis shows that PV‐TECS can be effectively used in photovoltaic power plants for efficiency enhancement with a gain in the range of 1%–22% for a monocrystalline PV module depending on location and type of integration. The study is of interest for further research to develop industrial applications.
Research Advances and Perspectives on Terahertz Detection based on 2D Materials
Authors: Chen Zhuoxuan , Li Zelong , Iqbal Muhammad Ahsan , Arif Nayab , Xing Chenyang , Qi Lu , Zeng Yu‐Jia 
Published: August 2024

AbstractTerahertz (THz) detection offers unique advantages in penetrating materials opaque to visible light and infrared radiation, which is crucial for applications in security, medical imaging, and material analysis. Despite challenges posed by a lack of suitable optical materials, recent strides in 2D materials, such as graphene, transition metal dichalcogenides (TMDCs), and topological materials, show promise in overcoming these limitations. This review critically examines the exceptional optical and electrical properties of 2D materials, and surveys recent advancements in 2D THz optoelectronics. Finally, the key challenges and prospects in this burgeoning field of research are discussed.
Lipopolysaccharide, arbiter of the gut–liver axis, modulates hepatic cell pathophysiology in alcoholism
Authors: Mak Ki M. , Shekhar Aditya C. 
Published: August 2024

AbstractOver the last four decades, clinical research and experimental studies have established that lipopolysaccharide (LPS)—a component of the outer membrane of gram‐negative bacteria—is a potent hepatotoxic molecule in humans and animals. Alcohol abuse is commonly associated with LPS endotoxemia. This review highlights LPS molecular structures and modes of release from bacteria, plasma LPS concentrations, induction of microbiota dysbiosis, disruption of gut epithelial barrier, and translocation of LPS into the portal circulation impacting the pathophysiology of hepatic cells via the gut‐liver axis. We describe and illustrate the portal vein circulation and its distributaries draining the gastrointestinal tract. We also elaborate on the gut‐liver axis coupled with enterohepatic circulation that represents a bidirectional communication between the gut and liver. The review also updates the data on how circulating LPS is cleared in a coordinated effort between Kupffer cells, hepatocytes, and liver sinusoidal endothelial cells. Significantly, the article reviews and updates the modes/mechanisms of action by which LPS mediates the diverse pathophysiology of Kupffer cells, hepatocytes, sinusoidal endothelial cells, and hepatic stellate cells primarily in association with alcohol consumption. Specifically, we review the intricate linkages between ethanol, microbiota dysbiosis, LPS production, gut‐liver axis, and pathophysiology of various hepatic cells. The maintenance of the gut barrier structural and functional integrity and microbiome homeostasis is essential in mitigating alcoholic liver disease and improving liver health.
Relationship Between Ultrasound and Physical Examination in the Assessment of Enthesitis in Patients With Spondyloarthritis: Results From the DEUS Multicenter Study
Authors: Di Matteo Andrea , Di Donato Stefano , Smerilli Gianluca , Becciolini Andrea , Camarda Federica , Cauli Alberto , Cazenave Tomás , Cipolletta Edoardo , Corradini Davide , de Agustin Juan Jose , Destro Castaniti Giulia M. , Di Donato Eleonora , Duran Emine , Farisogullari Bayram , Fornaro Marco , Francioso Francesca , Giorgis Pamela , Granados Raquel , Granel Amelia , Hernandez‐Diaz Cristina , Horvath Rudolf , Hurnakova Jana , Jesus Diogo , Karadag Omer , Li Ling , Li Yang , Lommano Maria G. , Marin Josefina , Martire María V. , Michelena Xabier , Muntean Laura , Piga Matteo , Rosemffet Marcos , Rovisco João , Salaffi Fausto , Saraiva Liliana , Scioscia Crescenzio , Tamas Maria‐Magdalena , Tanimura Shun , Venetsanopoulou Aliki , Ventura Rios Lucio , Villota Orlando , Villota‐Eraso Catalina , Voulgari Paraskevi V. , Vukatana Gentiana , Zacariaz Hereter Johana , Grassi Walter , Filippucci Emilio 
Published: August 2024

ObjectiveThe study objectives were (i) to explore the agreement between the Outcome Measures in Rheumatology (OMERACT) ultrasound lesions of enthesitis and physical examination in assessing enthesitis in patients with spondyloarthritis (SpA) and (ii) to investigate the prevalence and clinical relevance of subclinical enthesitis in this population.MethodsTwenty rheumatology centers participated in this cross‐sectional study. Patients with SpA, including axial spondyloarthritis (axSpA) and psoriatic arthritis (PsA), underwent both ultrasound scan and physical examination of large lower limb entheses. The OMERACT ultrasound lesions of enthesitis were considered, along with a recently proposed definition for “active enthesitis” by our group. Subclinical enthesitis was defined as the presence of “active enthesitis” in ≥1 enthesis in patients with SpA without clinical enthesitis (ie, number of positive entheses on physical examination and Leeds Enthesitis Index score = 0).ResultsA total of 4,130 entheses in 413 patients with SpA (224 with axSpA and 189 with PsA) were evaluated through ultrasound and physical examination. Agreement between ultrasound and physical examination ranged from moderate (ie, enthesophytes) to almost perfect (ie, power Doppler and “active enthesitis”). Patellar tendon entheses demonstrated the highest agreement, whereas Achilles tendon insertion showed the lowest. Among 158 (38.3%) of 413 patients with SpA with clinical enthesitis, 108 (68.4%) exhibited no “active enthesitis” on ultrasound. Conversely, of those 255 without clinical enthesitis, 39 (15.3%) showed subclinical enthesitis. Subclinical enthesitis was strongly associated with local structural damage. However, no differences were observed regarding the demographic and clinical profiles of patients with SpA with and without subclinical enthesitis.ConclusionOur study underscores the need for a comprehensive tool integrating ultrasound and physical examination for assessing enthesitis in patients with SpA.image
Pushing the TAD boundary: Decoding insulator codes of clustered CTCF sites in 3D genomes
Authors: Huang Haiyan , Wu Qiang 
Published: August 2024

AbstractTopologically associating domain (TAD) boundaries are the flanking edges of TADs, also known as insulated neighborhoods, within the 3D structure of genomes. A prominent feature of TAD boundaries in mammalian genomes is the enrichment of clustered CTCF sites often with mixed orientations, which can either block or facilitate enhancer–promoter (E‐P) interactions within or across distinct TADs, respectively. We will discuss recent progress in the understanding of fundamental organizing principles of the clustered CTCF insulator codes at TAD boundaries. Specifically, both inward‐ and outward‐oriented CTCF sites function as topological chromatin insulators by asymmetrically blocking improper TAD‐boundary‐crossing cohesin loop extrusion. In addition, boundary stacking and enhancer clustering facilitate long‐distance E‐P interactions across multiple TADs. Finally, we provide a unified mechanism for RNA‐mediated TAD boundary function via R‐loop formation for both insulation and facilitation. This mechanism of TAD boundary formation and insulation has interesting implications not only on how the 3D genome folds in the Euclidean nuclear space but also on how the specificity of E‐P interactions is developmentally regulated.
Biomedical application of microalgal‐biomaterials hybrid system
Authors: Li Yize , Fan Yali , Ye Shuo , Xu Lingyun , Wang Gezhen , Lu Yuli , Huang Suxiang , Zhang Yingying 
Published: August 2024

AbstractMicroalgae are a group of microorganisms containing chlorophyll A, which are highly photosynthetic and rich in nutrients. And they can produce multiple bioactive substances (peptides, proteins, polysaccharides, and fatty acids) for biomedical applications. Despite the unique advantages of microalgae‐based biotherapy, the insufficient treatment efficiency limits its further application. With the development of nanotechnology, the combination of microalgae and biomaterials can improve therapeutic efficacies, which has attracted increasing attention. In this microalgal‐biomaterials hybrid system, biomaterials with excellent optical and magnetic properties play an important role in biological therapy. Microalgae, as a natural vehicle, can increase oxygen content and alleviate hypoxia in diseased areas, further enhancing therapeutic effects. In this review, the synergistic therapeutic effects of microalgal‐biomaterials hybrid system in different diseases (cancer, myocardial infarction, ischemia stroke, chronic infection, and intestinal diseases) are comprehensively summarized.