bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stable Mono‐Radical and Triplet Diradicals Based on Allylic Radical‐Embedded All‐Benzenoid Polycyclic Hydrocarbons
Authors: Wang Lei , Niu Weiwei , Tian Di , Jiao Tianyu , Zhang Lemin , Hou Xudong , Han Yi , Zou Ya , Wu Jishan , Li Guangwu 
Published: November 2024

AbstractHigh‐spin organic radicals are notable for their unique optical, electronic, and magnetic properties, but synthesizing stable high‐spin systems is challenging due to their inherent reactivity. This study presents a novel strategy for designing stable high‐spin polycyclic hydrocarbons (PHs) by incorporating allylic radical into fused aromatic benzenoid rings. To enhance stability, large steric hindrance groups with a synergistic captodative effect were added to the allylic radical centers. This approach was applied to synthesize derivatives of two open‐shell all‐benzenoid PHs: benzo[fg]tetracene (1) and dibenzo[fg,lm]heptacene (2). Both compounds exhibited excellent stability, with diradical 2 showing a half‐life of up to 17.2 days under ambient conditions. Bond length analysis and theoretical calculations suggest that 1 and 2 predominantly feature Clar's aromatic sextet structures with embedded allylic radicals. Compound 2 was confirmed to have a triplet ground state through DFT calculations and experimental methods, including pulse EPR spectroscopy and SQUID measurements. This work introduces a new design strategy for stable high‐spin hydrocarbons, paving the way for future developments in high‐spin organic materials.
Metabolic Acidity/H2O2 Dual‐Cascade‐Activatable Molecular Imaging Platform Toward Metastatic Breast Tumor Malignancy
Authors: Dou Kun , Lu Jiao , Xing Yanlong , Wang Rui , Won Miae , Kim Jungryun , Yu Fabiao , Seung Kim Jong 
Published: November 2024

AbstractFluorescence imaging in the second near‐infrared window (NIR‐II) is crucial for accurate tumor diagnosis, offering superior resolution and penetration capabilities. Current NIR‐II probes are limited by either being “always on” or responding to one stimulus, leading to low signal‐to‐noise ratios and potential false positives. We introduced a dual‐lock‐controlled probe, HN‐PBA, activated by both H2O2 and tumor acidic environment. This dual response ensures bright fluorescence at tumor sites, leading to higher tumor‐to‐normal tissue ratios (T/NT) compared to conventional “always on” probes and probes activated only by H2O2. This strategy allows precise tumor identification and removal of primary and metastatic tumors, achieving superior T/NT ratios (24.3/6.4 for orthotopic and lung metastasis, respectively). Our probe also effectively detected lung metastatic foci as small as≤0.7 mm and showed the capability for accurate lesion localization in clinical breast cancer specimens. This dual‐stimuli‐responsive strategy could aid future diagnostic probe design.
Internal Electron‐Donation Allocation Design for Intrinsic Solubilization of Lithium Nitrate in Ester Electrolyte for Stable Lithium Metal Batteries
Authors: Gu Sheng , Zhang Yu , Li Meng , Lin Qianru , Xu Guoqi , Zhang Naiqing 
Published: November 2024

AbstractLithium metal batteries (LMBs) have become a hot topic in the research of next‐generation advanced battery technology due to their high specific energy. However, the high reaction activity between lithium metal and electrolyte is considered one of the key bottlenecks limiting large‐scale applications of LMBs. As a classic electrolyte additive, lithium nitrate (LiNO3) significantly improves the stability of lithium metal in ether‐based electrolytes. However, its solubility in carbonate‐based electrolytes widely used in lithium‐ion batteries is extremely low, causing limited protective capability on lithium metal, which has become a key obstacle to the commercial application of lithium metal batteries. Here, we enhanced the local negative charge density of carbonyl oxygen atoms in carbonate molecules by introducing electron donors, making it easier for them to coordinate with Li+, thereby weakening the interaction between Li+ and NO3−, and significantly increasing the solubility of LiNO3 in ester electrolytes. The modified ester solvent promotes the derivatization and decomposition of salt anions, leading to the formation of a dense SEI layer rich in LiF and LiNxOy. This significantly improves the stability of lithium metal in ester‐based electrolytes. The assembled Li||Li symmetric battery shows excellent cycling performance of over 4000 hours.
Enantioconvergent Negishi Cross‐Couplings of Racemic Secondary Organozinc Reagents to Access Privileged Scaffolds: A Combined Experimental and Theoretical Study
Authors: Preinfalk Alexander , Oost Rik , Menger Maximilian F. S. J. , Simaan Marwan , Lemouzy Sébastien , Senoner Samuel , Shaaban Saad , Maryasin Boris , González Leticia , Maulide Nuno 
Published: November 2024

AbstractAn enantioconvergent palladium‐catalyzed Negishi cross‐coupling with racemic secondary organozinc reagents has been developed, enabling access to enantioenriched 1,1‐diarylalkane motifs in high yields and enantioselectivities. Computational data indicates that the racemization of organozinc compounds most likely occurs through a bridged bimolecular mechanism.
Controllable Graphene/MoS2 Heterointerfaces by Perpendicular Surface Functionalization
Authors: Cao Qing , Dai Jiajun , Hao Zhuting , Paulus Beate , Eigler Siegfried , Chen Xin 
Published: November 2024

AbstractSurface chemistry and interface interactions profoundly influence the properties of two‐dimensional (2D) materials and heterostructures. Therefore, developing methods to precisely control surfaces and interfaces is crucial for harnessing the properties and functions of 2D materials and heterostructures. Here, we developed a facile approach to tuning the interface distance and properties of graphene/MoS2 heterostructures (G/MoS2) by varying the functional groups attached to the surface of graphene bottom layer. We systematically investigated how different functionalized graphene bottom layers affect the interlayer distance, coupling between the interlayers, and optical properties of resulting G/MoS2 heterostructures. Our findings indicate that both the size and electron‐withdrawing/donating properties of functional groups are pivotal in regulating charge transport properties, with size playing a particularly decisive role. Our approach demonstrates an efficient and flexible pathway to regulate the interlayer spacing and charge transport, highlighting the potential of engineering interface chemistry in optimizing properties of van der Waals heterostructures.
Reducing Dead Species by Electrochemically‐Densified Cathode‐Interface‐Reaction Layer towards High‐Rate‐Endurable Zn||I‐Br Batteries
Authors: Feng Zhenfeng , Tang Yongchao , Wei Yue , He Jiangfeng , Liu Guigui , Yan Jianping , Qi Jintu , Shi Zhiheng , Yang Qi , Wen Zhipeng , Ye Minghui , Zhang Yufei , Liu Xiaoqing , Chao Li Cheng 
Published: November 2024

AbstractInterhalogen‐involved aqueous Zn||halogen batteries (AZHBs) are latent high‐energy systems for grid‐level energy storage, yet usually suffer from poor high‐rate endurability caused by the formation of “dead species”. Herein, via an electrochemically‐densified cathode‐interface‐reaction layer (CIRL), Zn||I−Br batteries involving interhalogen reactions between the I2 cathode and Br− from the electrolytes are initially achieved with excellent high‐rate endurability. Different from that in diluted electrolytes, the CIRL formed in Br−‐concentrated electrolyte is denser and water‐lean, which enables halogen species conversion with a more rapid charge transfer and lower activation energy. More importantly, the CIRL robustly affords a decent I2 conservation by accelerated conversion kinetics and limited species diffusion, thereby endowing the Zn||I−Br batteries with an ultralong high‐rate lifespan. The electrochemical mechanism is sufficiently verified by multiple spectral characterizations. Consequently, Zn||I−Br batteries in Br−‐concentrated (20 m) electrolytes exhibit an overwhelming rate capability and lifespan to those in Br−‐diluted (2 m) electrolytes. Typically, when cycled at a large current density of 10 A g−1, an ultralong lifespan of over 25,000 cycles is achieved with a high retention of 98.3 %. This study provides new insight into the CIRL‐dictated active species conservation for high‐rate endurable AZHBs, which could apply to other high‐energy interhalogen batteries.
Total Synthesis and Configuration Assignment of (+)‐Myxoquaterine‐450
Authors: Löhr Johanna , Ortmann Sabrina , Popoff Alexander , Müller Rolf , Bach Thorsten 
Published: November 2024

AbstractMyxoquaterines represent a recently discovered class of natural products with intriguing biological properties. They were isolated from Pendulasporacea albinea MSr 11954 and display a unique structure combining heterocyclic (pyrrole, oxazoline), hexaene, and 2‐amino‐1,3‐diol subunits. We have now synthesized the first example of a myxoquaterine natural product, myxoquaterine‐450, in a highly convergent fashion, in which the sensitive hexaene unit was established in the final stages of the synthesis (16 linear steps starting from l‐serine). Comparison of the synthetic material with an authentic sample allowed to establish and confirm the constitution and configuration of the natural product.
Photon‐Driven Dye Induction Pyroptosis: An Emerging Anti‐Tumor Immunotherapy Paradigm
Authors: Zeng Shuang , Wang Jingyun , Kang Heemin , Li Haidong , Peng Xiaojun , Yoon Juyoung 
Published: November 2024

AbstractPhotoimmunotherapy represents a novel and promising modality in anti‐tumor immunotherapy, offering new hope in the realm of cancer treatment due to its distinctive mechanism and substantial therapeutic efficacy. This innovative approach synergistically integrates photon technology with immunological principles, utilizing photon energy to activate the body's immune response. Photon‐driven pyroptosis, a pivotal element of photoimmunotherapy, has significantly revitalized the advancement of this discipline. To support this critical progress, this minireview offers an exhaustive examination of the organic dyes presently employed for photon‐driven pyroptosis, alongside an analysis of the prevailing challenges and opportunities in dye molecule design. It is our aspiration that this minireview will contribute to the acceleration of developments in photon‐driven pyroptosis dye and the broader field of photoimmunotherapy.
Shape‐Selective Zeolites for Tandem CO2 Hydrogenation‐Carbonylation Reactions
Authors: Van Dessel Hendrik , Van Minnebruggen Sam , Dedapper Jasper , Paciok Paul , Usoltsev Oleg , Krajnc Andraž , Bugaev Aram , De Vos Dirk E. 
Published: November 2024

AbstractThe valorization of carbon dioxide as a C1 building block in C−C bond forming reactions is a critical link on the road to carbon‐circular chemistry. Activation of this inert molecule through reduction with H2 to carbon monoxide in the reverse water‐gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite‐based compartmentalized approach. More specifically, Pt encapsulated in a small‐pore LTA zeolite selectively generates carbon monoxide in mild reaction conditions; an ensuing one‐pot carbonylation reaction allows to shift the equilibrium through continuous consumption of CO. Moreover, the zeolite encapsulation avoids undesired reactions like hydrogenation of the olefin reactant through a molecular sieving effect. This strategy was first studied in‐depth for Rh‐catalyzed olefin hydroformylation with CO2/H2, affording aldehydes in good yields with high regioselectivities. The methodology was then extended to a variety of carbonylations using CO2 for the synthesis of bulk and fine chemicals.
Real‐Time Adaptive Inline Acidification Enhances Continuous pH Control for Viral Inactivation
Authors: Lee Jia Sheng Zach , Nguyen Tan Dai , Zheng Zi Ying , Zhang Wei , Liu Dan 
Published: November 2024

ABSTRACTExisting low pH viral inactivation methods for continuous downstream processing of biologics typically rely on predictive models to estimate the necessary pH adjustments. However, these methods are of limited use during the process development stage due to the dynamic nature of capture chromatography, where batch variations can alter the eluted protein titer. This study introduces an inline viral inactivation system (IVIS) that utilizes real‐time adaptive control and inline sensor readings to precisely regulate the pH manipulation for inline acidification and continuous viral inactivation. The IVIS, which includes a coiled flow inversion reactor (CFIR), is integrated with a multicolumn capture chromatography system to demonstrate a fully continuous process from protein capture chromatography to inline pH manipulation. The system achieved precise inline pH manipulation within ±0.15 and a narrow residence time distribution of 13.5 min with a relative width of 0.7. The introduction of real‐time inline pH manipulation with the IVIS signifies a notable advancement in managing critical process parameters (CPPs) and ensuring consistent product quality across varied production environments for continuous downstream bioprocessing.
Exploring Online Teaching's Impact on Instructors in Core Engineering Courses: Insights, Challenges, and Future Directions
Authors: Alqudah Rajaa , Batarseh Majd , El‐Issa Fadia 
Published: November 2024

ABSTRACTThis study examines the impact of online teaching on instructors of fundamental engineering courses, focusing on insights, challenges, and future pathways. By analyzing the instructors' perspectives, the research examines various aspects of online teaching, including mode of delivery, student engagement strategies, assessment preferences, and future directions. Insights are drawn from a comprehensive survey of instructors, shedding light on their experiences, challenges, and preferences in the online teaching landscape. The findings highlight a preference for synchronous sessions, the utilization of diverse engagement techniques, and the significance of maintaining academic integrity in assessments. Instructors' preference for face‐to‐face interaction for improved academic performance and openness to hybrid teaching modes are evident. This study not only provides valuable insights into the dynamics of online teaching but also paves the way for future advancements in pedagogical strategies and educational technology integration. The research identifies potential areas for future work, ranging from refining hybrid teaching models to exploring emerging technologies and fostering instructor training.
The Prognostic and Risk Factors for Children With High‐Risk Mature B‐Cell Non‐Hodgkin's Lymphoma: A Retrospective Multicenter Study
Authors: Wang Xiaoming , Ding Luping , Fang Yongjun , Yan Jie , Gao Ju , Yang Liangchun , Liu Aiguo , Lu Jun , Wang Jingfu , Zhang Aijun , Gao Yijin , Ju Xiuli 
Published: November 2024

ABSTRACTBackgrounds and AimsOur previous study (CCCG‐BNHL‐2015) reported the treatment strategies and outcomes of pediatric B‐cell non‐Hodgkin's lymphoma (B‐NHL) in China which showed that children in low‐risk groups already have a dramatically favorable prognosis. However, for high‐risk groups, the prognosis still needs to be improved. In this study, we aimed to identify the factors influencing prognosis in high‐risk groups (stage III and stage IV).ResultsOur results revealed that gender, lactate dehydrogenase (LDH) level, stage at the time of diagnosis, and early complete remission (CR) achievement were significant factors influencing prognosis (p < 0.05). The 3‐year EFS rate for R4 group patients without rituximab treatment was only 25.0% ± 20.4%. Among all patients in stage IV, the 5‐year EFS rates for those with involvement of only bone marrow (BM) or central nervous system (CNS) were 83.0% ± 4.5%, 81.8% ± 8.2%, but the 5‐year EFS rates for those with both BM and CNS involved were only 37.5% ± 15.3% (p = 0.002). For stage III patients with LDH ≥ 4N, the 5‐year EFS rates for those achieving CR and those not achieving CR after 2 treatment cycle were 88.9% ± 5.2% and 67.9% ± 7.3%(p = 0.036).ConclusionsTherefore, R4 group patients benefited from rituximab treatment. However, children at stage III, LDH ≥ 4N not achieving CR after the 2nd treatment cycle, and those with both BM and CNS involved are still at a very high risk of treatment failure. This study serves as a crucial reference for optimizing risk stratification, refining treatment categorizations, and optimizing treatment protocols.
Bridging Real and Virtual: An Ecological Approach to Prevent Cyberviolence Against Women
Authors: Agueli Barbara , Esposito Ciro , Carnevale Stefania , Arcidiacono Caterina , Di Napoli Immacolata 
Published: November 2024

ABSTRACTWomen experience gender violence more than men, in the digital world as well as offline. To understand and prevent this phenomenon, we must consider the continuum between the virtual and the real world and highlight that cyberviolence and offline violence follow the same patterns. Therefore, to comprehend cyberviolence against women, the present study aimed to examine the feelings and emotions of those who have had direct and indirect experiences with it. The research involved 43 young Italians, aged 20–35 and used a narrative approach with a stimulus composed of six questions. The textual material was analysed using reflexive thematic analysis and four main themes emerged: Emotional experiences of cyberviolence; the amplification of cyberviolence in the offline world; the role of bystanders; and actions to prevent cyberviolence. The results highlighted the importance of approaching cyberviolence against women from a holistic and multidimensional perspective through an ecological approach that integrates different levels of action: collective, organisational, interpersonal and individual. Cyberviolence against women entails interventions that are complex and multi‐focused on all those who inhabit the virtual dimension, as well as the offline dimension, where the consequences of online violence become evident.
Therapeutic Potential of Rare Sesterterpenoids from Aspergillus Variecolor Strain SDG and Docking Studies
Authors: Kumar Koochana Pranay , Rao Annam S. CH. V. Appa , Sunkara Kavya , Fariha Umme Ummarah , Rajeswari Batchu Uma , Misra Sunil , Gowri Ponnapalli Mangala 
Published: November 2024

AbstractEthyl acetate extract of the cultures of the soil‐derived filamentous fungus, Aspergillus variecolor SDG strain from Nallamala forest resulted in the isolation of extremely rare sesterterpenoids, stellatic acid (1) and andilesin C (2). We report a thorough chemical characterization of these compounds using various spectroscopic techniques and evaluation of their in vitro preclinical therapeutic potential. Stellatic acid exhibits potent antioxidant activity with an IC50 of 38 μg/mL and significant anticancer activity against HeLa, HepG2, MCF7, and A549 cancer cell lines with an IC50 of 7–12 μM. On the other hand, andilesin C displayed moderate cytotoxicity against DU145 and B16F10 cancer cell lines but lacked antioxidant activity. Furthermore, the potential hypoglycemic property of stellatic acid was evaluated by measuring its inhibitory effect against α‐glucosidase. It exhibited tenfold potency against yeast α‐glucosidase (IC50 101.73 μg/mL) than mammalian α‐glucosidase (IC50 1000.00 μg/mL). Docking studies were also performed to suggest the interaction mode of stellatic acid in the α‐glucosidase enzyme active site. Notably, yeast α‐glucosidase shows a higher affinity towards stellatic acid than mammalian α‐glucosidase (3TOP). Thus, the in vitro preclinical study of stellatic acid suggests its potential efficacy in therapeutic drug development.
Chemometrics: A Vital Implement for Understanding the Water Structures by Near‐Infrared Spectroscopy
Authors: Wang Haipeng , Han Li , Cai Wensheng , Shao Xueguang 
Published: November 2024

ABSTRACTWater structures take an important role in chemical and biological systems, because the structure and function of a molecule may depend on the structure of water with which the molecule interacts. Near‐infrared (NIR) spectroscopy has been proven to be powerful in analyzing the structure of water due to its sensitive response to OH. However, chemometrics is vitally important in the analysis of NIR spectrum of water due to the low resolution of the spectrum and the complexity of the water structures. In this review, chemometric methods for structural analysis of water in aqueous systems, particularly in chemical and biological processes, by NIR spectroscopy were summarized, from the improvement of spectral resolution to the effective extraction of the spectral information of different water structures. Through the changes of the spectral features of the water structures, the structural transformation of proteins, thermo‐responsive polymers, antifreeze agents, as well as the structural variation of water in the transformation were elucidated. Water was proved to be a good probe for analyzing the structure and interactions in aqueous solutions and chemical/biological processes by NIR spectroscopy.
A Comprehensive Review on the Biofilm‐Mediated Removal of Nitrogen and Chemical Oxygen Demand From Different Wastewater Sources
Authors: Misra Modhurima , Das Pranati , Mehra Anshita , Chattopadhyay Soham 
Published: November 2024

ABSTRACTDischarging effluents with high chemical oxygen demand (COD) and nitrogen content into the environment threatens human and aquatic life. An increase in nitrogen load results in depletion of dissolved oxygen (DO), eutrophication, ecological stress, and biodiversity loss. Intake of water containing excess nitrate can cause different diseases. Conventional physicochemical nitrogen removal techniques are expensive and also generate secondary pollutants. In contrast, biological methods offer effective and economical outcomes with global acceptance. Biofilm‐based techniques have the advantages of low space requirement, resistance toward toxic shocks, and absence of sludge backflow. The carriers used in biofilm reactors allow the growth of heterogeneous microbial consortia, which can simultaneously remove COD, nitrogenous compounds, and phosphates. This review aims to summarize the outcomes of the individual lab‐scale research in this area, critically analyze the scientific findings, and understand the research gap. Conventional nitrification–denitrification and anammox have often been replaced by more efficient approaches such as simultaneous nitrification–denitrification, partial nitrification–denitrification, partial nitritation and anammox, and simultaneous partial nitrification, anammox, and denitrification. Multistage moving bed biofilm reactors have been specially designed with step feeding for complete nitrogen removal. Through anammox in a sequencing batch reactor, a high rate of denitrification could be obtained, whereas simultaneous nitrification–denitrification using a membrane bioreactor resulted in almost complete removal of nitrogen. We expect that this review will provide the direction for designing experiments on enhanced removal of nitrogen and COD from different wastewater sources using microbial biofilms.