bluuebunny/crossref_metadata_2025_split huggingface dataset:
In‐Situ Constructed Core‐Shell Catalyst Enabling Subzero Capacity Unlocking of Cost‐Effective and Long‐Life Vanadium Flow Batteries
Authors: Nie Yizhe , Nie Rui , Lin Hao , Wu Jiajun , Yu Lihong , Liu Le , Xi Jingyu 
Published: December 2024

AbstractVanadium flow battery (VFB) promises a route for achieving grid‐scale power storage by harnessing renewable energy sources. However, the sluggish reaction kinetics of vanadium redox couples and serious hydrogen evolution reaction (HER) still restrict the further development of VFB. Addressing these challenges requires not only effective solutions but also ones that are cost‐efficient and scalable to meet the demands of affordable energy storage. Here, we present an in situ constructed Cu@Cu6Sn5 core‐shell catalyst by incorporating metal ions into the electrolyte. The Cu core, encapsulated by the Cu6Sn5 shell, forms an excellent conductive pathway to the graphite felt electrode. Charge transfer between Cu and Sn within Cu6Sn5 shell accelerates the reaction kinetics of V2+/V3+ redox couple and selectively inhibits HER, as confirmed through in situ weak measurement imaging method. The Cu@Cu6Sn5 battery achieves a peak power density of 1119.1 mW cm−2 at 1350 mA cm−2, operates stably for 1200 cycles without catalyst failure, and is available over a wide‐temperature range. Furthermore, we identify a demand of subzero capacity unlocking. Achieving a 23.4 % theoretical capacity unlocking at −10 °C with a cut‐off voltage up to 1.75 V, bespeaking a crucial breakthrough toward cost‐effective VFB.
Thermal Modulation of Exciton Recombination for High‐Temperature Ultra‐Long Afterglow
Authors: Jiang Ping , Ding Bingbing , Yao Jiayi , Zhou Lei , He Zhenyi , Huang Zizhao , Yin Chenjia , Tian He , Ma Xiang 
Published: December 2024

AbstractDeveloping smart materials with tunable high‐temperature afterglow (HTA) luminescence remains a formidable challenge. This study presents a metal‐free doping system using boric acid as matrix and polycyclic aromatic hydrocarbons as dopants. This composition achieves dynamically tunable afterglow combining a bright blue HTA lasting for over ten seconds even at 150 °C and an ultra‐long yellow room‐temperature phosphorescence below 110 °C. The observed HTA is attributed to the thermally released exciton recombination within the dopant molecules, which shows excellent temperature tolerance compared to traditional triplet related phosphorescence and thermally activated delayed fluorescence. The planarity of dopants is extensively investigated playing a pivotal role in modulating Dexter electron transfer (ET) for capturing released electrons and thereby affecting the overall performance of tunable HTA. This work provides an efficient and universal doping strategy to engineer tunable HTA through the synergistic action of thermally releasing electrons, Dexter ET and exciton recombination.
Cleavage and Reassembly of 1,3‐Dicarbonyls with Enaminones to Synthesize Highly Functionalized Naphthols
Authors: Zhou Shuguang , Liu Xin , Zhang Tao , Loh Teck‐Peng , Tian Jie‐Sheng 
Published: December 2024

AbstractThe cleavage of carbon‐carbon bonds and their subsequent reassembly into highly functionalized and useful molecules in an atom‐efficient manner has always been a central focus in the realm of organic synthesis. In this report, we describe the construction of highly functionalized naphthol esters via a tandem reassembly process, driven by Ullmann‐type coupling of enaminones and 1,3‐dicarbonyl compounds. Mechanistic investigations suggest the involvement of C(sp2)‐C(sp3) coupling, cyclization, two acyl migrations, aromatization, and additional transformations within this tandem sequence. This methodology offers several notable advantages, such as the use of inexpensive and easily accessible starting materials, the elimination of the need for expensive transition metal catalysis, simple operation in the atmosphere, exceptional compatibility with a wide range of substrates, and ease of conversion into drug scaffolds.
Cooperative Multiscale‐Assembly for Directional and Hierarchical Growth of Highly Oriented Porous Organic Cage Single‐Crystal Microtubes and Arrays
Authors: Liu Si‐Hua , Zhao Ke , Zhou Jun‐Hao , Dong Kang , Ai Hui , Liu Pai , Cui Jing‐Wang , Zhang Yun‐Hong , Puigmartí‐Luis Josep , Sun Jian‐Ke 
Published: December 2024

AbstractThe directional assembly of porous organic molecules into long‐range ordered architectures, featuring controlled hierarchical porosity and oriented pore channels with defined spatial arrangements, is a fundamental challenge in chemistry and materials science. Herein, using porous organic cages as starting units, we present a cooperative multiscale‐assembly strategy enabling the simultaneous alignment of pore channels and directional hierarchical growth in a single step. At the microscopic level, we employed double solvents to manipulate the intermolecular packing of microporous tetrahedral [4+6] imine cages (CC1 and CC3), resulting in pore channel orientation. Concurrently, at the mesoscopic level, convective flow in the double‐solvent system directed the spatial distribution of nuclei species, followed by diffusion limited growth, leading to the directional formation of single‐crystal microtubes. By precisely controlling the direction of convective flow, the nanocages were successfully organized into 2D and 3D single‐crystal microtube arrays while maintaining oriented micropores. This hierarchical porous architecture enhanced mass transfer, as confirmed by adsorption measurements. Interestingly, such 3D hierarchical microtube arrays can be utilized to immobilize Pd clusters and enzymes (lipase or Glucose oxidase) within the micro‐ and macropores, respectively, showing a 3.8‐ to 4‐fold enhancement in one‐pot tandem reaction activity compared to physical mixtures of individual analogues.
Synthesis of γ‐Amino Amides by Iridium‐Catalyzed Enantioselective Hydroamination of Internal Alkenes Directed by an Amide
Authors: Sun Yu‐Wen , Sun Xin , Tan Hao‐Tian , Li Bi‐Jie 
Published: December 2024

AbstractCatalytic regio‐ and enantioselective hydroamination of less activated internal alkenes presents a challenge to synthetic chemists due to their low reactivity and the difficulty in simultaneously controlling regio‐ and enantioselectivities. Here, we report an iridium‐catalyzed enantioselective hydroamination of internal alkenes directed by an amide. The amide group on the alkene effectively directs the catalyst to overcome the low reactivity and control the regioselectivity and the enantiotopic face selection. Phthalimide serves as the amination agent, which could be readily removed to afford a primary amine. This coordination assistance enables hydroamination to occur selectively at the remote position with up to 97 % ee, delivering valuable enantio‐enriched γ‐amino acid derivatives that are otherwise challenging to access.
Chemocatalytic Conversion of Dinitrogen to Ammonia Mediated by a Tungsten Complex
Authors: Vogt Anna‐Marlene , Engesser Tobias A. , Krahmer Jan , Michaelis Niels , Pfeil Mareike , Junge Jannik , Näther Christian , Le Poul Nicolas , Tuczek Felix 
Published: December 2024

AbstractWhereas molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase, corresponding tungsten complexes were in most cases found to be catalytically inactive. Herein, we present a modified pentadentate tetrapodal (pentaPod) phosphine ligand in which two dimethylphosphine groups of the pentaPodMe (P5Me) ligand have been replaced with phospholanes (Pln). The derived molybdenum complex [Mo(N2)P5Pln] generates 22 and the analogous tungsten complex [W(N2)P5Pln] 7 equivalents of NH3 from N2 in the presence of 180 equivalents of SmI2(THF)2/H2O, rendering the latter the first tungsten complex chemocatalytically converting N2 to NH3. In contrast, the tungsten complex [W(N2)P5Me] generates ammonia from N2 only in a slightly overstoichiometric fashion. The reasons for these reactivity differences are investigated with the help of spectroscopic and electrochemical methods.
Fluoromethyl Triflate and Fluoromethyl Fluorosulfonate: Easily Accessible and Powerful Fluoromethylation Reagents
Authors: Gisnapp Alexander , Trapp Pia C. , Schwabedissen Jan , Stammler Hans‐Georg , Reichel Marco , Leitz Dominik , Krumm Burkhard , Karaghiosoff Konstantin , Mitzel Norbert W. 
Published: December 2024

AbstractFluoromethyl triflate (superfluoromethyl, SFM, FH2COSO2CF3) and fluoromethyl fluorosulfonate (magic fluoromethyl, MFM, FH2COSO2F) are two easily synthesized, highly effective and non‐ozone depleting fluoromethylation reagents. They are analogous to the well‐known and widely used methylation reagents H3COSO2CF3 and H3COSO2F. Both SFM and MFM have been fully characterized by multinuclear NMR spectroscopy (1H, 13C, 17O, 19F, 33S). Their structures have been determined in the solid state on in situ grown crystals by X‐ray diffraction and in the gas phase by electron diffraction. The fluoromethylation efficiency of SFM and MFM was shown by reactions with chalcogen nucleophiles of differing nucleophilicity. All fluoromethylated products were isolated as pure compounds and characterized by NMR and vibrational spectroscopy, as well as in some cases by single crystal X‐ray diffraction.
Changes in phytochemicals, antioxidant activities, and oxidative stability of oil from germinated peanuts
Authors: Huh Moon Haeng , Lee Junsoo , Lee Hana 
Published: December 2024

AbstractGermination is a promising technique for enhancing the nutritional and functional properties of seeds. Among the nuts, peanuts are composed of approximately 50% oil, which is abundant in unsaturated fatty acids, tocopherols, and phytosterols. This study investigated the changes in phytochemical profile, antioxidant capacity, and oxidative stability of oil from germinated peanuts. Peanuts were germinated over 0, 2, 4, 6, and 8 days. The oil from germinated peanuts exhibited increased levels of α‐tocopherol, phytosterols, and carotenoids, while the γ‐tocopherol, oleic acid, and linoleic acid levels were reduced. Notably, the oil from germinated peanuts at Day 8 exhibited substantially improved antioxidant activity and oxidative stability compared with oil from ungerminated peanuts. These enhancements were attributed to the elevated phytochemical content of the peanut oil resulting from germination. These results highlight that germination of peanut seeds is an effective strategy for enhancing peanut oil's phytochemical content and oxidative stability, thereby presenting potential benefits for health‐conscious consumers.
Multichromophoric Triad and g‐C3N4 Composite as Efficient Heterogeneous Photocatalyst for Oxidative Amidation of Aldehydes
Authors: Kumari Anita , Sekhar Roy Raj , Gautam Ujjal K. , Sengupta Sanchita 
Published: December 2024

AbstractIn this work, we have synthesized a multichromophoric light‐harvesting antenna, namely, triad, consisting of naphthalene monoimide (NMI) and perylene monoimide (PMI) chromophores. Triad was adsorbed onto polymeric graphitic carbon nitride (g‐C3N4) to form triad/g‐C3N4 composite, utilized as a photocatalyst for oxidative amidation reaction. This composite photocatalyst demonstrated enhanced photocatalytic activity for the conversion of a variety of aldehydes to amides, leading up to 82 % product yield compared to only g‐C3N4 or only triad as photocatalysts. This study highlights the potential of heterogeneous photocatalyst based on metal‐free multichromophoric systems for visible‐light‐driven amide bond formation through an environmentally benign approach.
Lithium in drinking water: Review of chemistry, analytical methods, and treatment technologies
Authors: Korak Julie A. , Brandhuber Philip J. , Goodwill Joseph E. 
Published: December 2024

AbstractLithium was included in the fifth Unregulated Contaminants Monitoring Rule, signaling the Environmental Protection Agency's interest in regulating lithium. Many questions regarding occurrence, health effects, and treatability of lithium exist. This review primarily focuses on the relationship between lithium chemistry and treatability. Sampling indicates nationwide lithium occurrence in drinking water. Yet, lithium is not included in the Integrated Risk Information System, reflecting a lack of censuses regarding its health effects. Aqueous lithium is a monovalent cation with size, charge density, and solubility properties that present treatment challenges. Lithium's growing economic value is stimulating new extraction and isolation technologies, but these may not be transferable to drinking water treatment. Currently, reverse osmosis is the only full‐scale drinking water treatment technology that can reliably remove significant levels (>50%) of lithium. Focusing future research efforts on electrodialysis and inorganic ion sieves may yield significant gains in effectiveness and readiness for the drinking water industry.
Integrative computational pipeline for identifying binding‐enhancing mutations targeting the MBD2–p66α interaction: Implications for therapeutic applications
Authors: Mazraedoost Sargol , Malekroodi Hadi Sedigh , Yi Myunggi , Liu J. Jay , In Lim Sung 
Published: December 2024

AbstractThis study presents a comprehensive computational pipeline to identify and evaluate potential stabilizing mutations for the coiled‐coil protein–protein interaction between methyl‐CpG‐binding domain protein 2 (MBD2) and transcriptional repressor p66‐alpha (p66α). The pipeline begins with the BeAtMuSiC program, which employs statistical potentials derived from known structures to predict candidate stabilizing mutations at the protein–protein interface. Out of 565 potential mutations, 10 single‐point mutations (K149I, K163I, A237F, K149L, K149M, K163L, R166M, R166W, K163F, and E155L) with the highest binding affinity were selected for further evaluation using rigorous alchemical free energy calculations. These alchemical simulations conducted using the double‐system/single‐box method, predicted changes in binding free energy (ΔΔG) upon mutation while maintaining charge neutrality. The Crooks–Gaussian intersection technique was employed to analyze the results, identifying K149I, K149L, and K163L as potentially enhancing binding affinity the most, while mutations like K163F, A237F, and E155L were predicted to destabilize the interaction significantly. Complementary conventional Molecular Dynamics Simulations provided further support for the alchemical predictions, revealing decreased flexibility, increased contacts, and more compact structures for the predicted stabilizing mutants compared with the wild‐type complex. Additionally, Molecular Mechanics Poisson–Boltzmann Surface Area (MM/PBSA) binding free energy calculations were performed, and their results were consistent with the direction of free energy change predicted by the alchemical approach. This multifaceted computational pipeline, combining predictive methods, alchemical simulations, and conventional analyses, offers valuable insights into modulating the binding affinity of the MBD2–p66α coiled‐coil interaction. The identified stabilizing mutations can create numerous opportunities across biotechnology, biomedical research, and synthetic biology.
Baihui‐Penetrating‐Qubin Acupuncture Attenuates Neurological Deficits Through SIRT1/FOXO1 Reducing Oxidative Stress and Neuronal Apoptosis in Intracerebral Hemorrhage Rats
Authors: Dong Shan‐Shan , Li Ming‐Yue , Yu Xue‐Ping , Kan Yu‐Na , Dai Xiao‐Hong , Zheng Lei , Cao Hong‐tao , Duan Wen‐Hui , Luo En‐Li , Zou Wei 
Published: December 2024

AbstractBackgroundIntracerebral hemorrhage (ICH) is a significant global disease with high mortality and disability. As of now, there is no effective therapy available. Oxidative stress and neuronal apoptosis play essential roles in ICH, determining neuronal survival. In our preliminary studies, we found that Baihui‐penetrating‐Qubin acupuncture could improve neurological deficits and neuropathological damage in the perihematomal area in ICH rats. The SIRT1/FOXO1 signaling pathway has been reported to mediate antioxidant and anti‐neuronal apoptosis. This study aimed to investigate the effects of Baihui‐penetrating‐Qubin acupuncture on oxidative stress and neuronal apoptosis after ICH and the role of SIRT1/FOXO1 in acupuncture's neuroprotection.MethodsICH rat models were established by autologous tail blood (50 µL) infusion into the caudate nucleus. EX527, SIRT1‐specific inhibitor was intraperitoneally administered 3 days before ICH. Baihui‐penetrating‐Qubin acupuncture treatment was performed once a day for 30 min after ICH. Neurological deficits were evaluated using the modified neurological severity score (mNSS). Brain edema was evaluated using brain water content. HE staining and Nissl staining were used to evaluate neuropathological damage in the perihematomal area. Terminal deoxynucleotidyl transferase dUTP nick end labeling was used to quantify neuronal apoptosis. Specific kits were used to detect the levels of SOD, CAT, GSH‐Px in the brain. The oxidative DNA damage was evaluated using enzyme‐linked immunosorbent assay to detect the level of 8‐hydroxyguanosine (8‐OHdG). Western blot was used to evaluate the expressions of SIRT1, Ac‐FOXO1, FOXO1, Bcl‐2, and Bax. Immunofluorescence staining was conducted to detect the cellular localization of SIRT1.ResultsBaihui‐penetrating‐Qubin acupuncture improved the neurological deficits and brain edema, reduced the pathological injury and neuronal degeneration in 3 days in the perihematomal area after ICH. Mechanistically, acupuncture reduced oxidative stress injury and neuronal apoptosis via activating SIRT1/FOXO1 pathway. The neuroprotective effects of acupuncture were abolished by injection of the SIRT1 inhibitor EX527.ConclusionsBaihui‐penetrating‐Qubin acupuncture could reduce oxidative stress and neuronal apoptosis, at least in part, through the SIRT1/FOXO1 signaling pathway, improving neurological deficits and neuropathological damage after ICH. These findings suggest that Baihui‐penetrating‐Qubin acupuncture is an effective therapy for ICH, as well as targeting SIRT1 signaling to promote neuron survival could be a potential therapeutic strategy.
Derivative Technologies of Expansion Microscopy and Applications in Biomedicine
Authors: Jia Dongling , Cui Minhui , Divsalar Adeleh , Khattab Tawfik A. , Al‐Qahtani Salhah D. , Cheung Edwin , Ding Xianting 
Published: December 2024

AbstractExpansion microscopy (ExM) is an innovative super‐resolution imaging technique that utilizes physical expansion to magnify biological samples, facilitating the visualization of cellular structures that are challenging to observe using traditional optical microscopes. The fundamental principle of ExM revolves around employing a specialized hydrogel to uniformly expand biological samples, thereby achieving super‐resolution imaging under conventional optical imaging conditions. This technology finds application not only in various biological samples such as cells and tissue sections, but also enables super‐resolution imaging of large biological molecules including proteins, nucleic acids, and metabolite molecules. In recent years, numerous researchers have delved into ExM, resulting in the continuous development of a range of derivative technologies that optimize experimental protocols and broaden practical application fields. This article presents a comprehensive review of these derivative technologies, highlighting the utilization of ExM for anchoring nucleic acids, proteins, and other biological molecules, as well as its applications in biomedicine. Furthermore, this review offers insights into the future development prospects of ExM technology.
High Catalytic Activity of Yttria‐Stabilized Zirconia‐Supported Gold Nanoparticles for Hydrogen Peroxide Production from Oxygen and Formic Acid Under Ambient Conditions
Authors: Teranishi Miwako , Naya Shin‐ichi , Tanaka Senku , Kobayashi Hisayoshi , Tada Hiroaki 
Published: December 2024

AbstractHydrogen peroxide (H2O2) is an important chemical widely used in the industry. Recently, insulating zirconia‐supported Au nanoparticles (NPs) prepared by a modified deposition precipitation method (Au/ZrO2‐MDP) have been reported to show catalytic activity for H2O2 production from aerated HCOOH aqueous solution much higher than Au/n‐type semiconducting metal oxides (Au/n‐MOs) prepared by the normal deposition precipitation method. In this study, we report that Au/yttria‐stabilized zirconia (Au/YSZ‐MDP) exhibits catalytic activity for the reaction far exceeding those of Au/n‐MOs and even Au/ZrO2‐MDP. Au/YSZ‐MDP yields H2O2 from the aerated 1.06 M HCOOH aqueous solution with an initial rate of 2.2 mmol h−1 gcat−1, and a turnover frequency (TOF) of 4.3 × 102 h−1 at 25 °C. X‐ray photoelectron and photoluminescence spectral data, in addition to the effect of YSZ surface modification with an aluminum oxide, indicate that the remarkable catalytic activity of Au/YSZ‐MDP is induced by the oxygen vacancies (Ov) and Ov‐derived Zr─OH groups on the YSZ surface in the vicinity of Au NPs.
Translational Medicine in Alzheimer's Disease: The Journey of Donanemab From Discovery to Clinical Application
Authors: Jayaprakash Nandhini , Elumalai Karthikeyan 
Published: December 2024

ABSTRACTSubstantial research has been conducted to identify an efficient treatment for Alzheimer's disease (AD). Existing treatments, including cholinesterase inhibitors and N‐methyl D‐aspartate (NMDA) receptor antagonists, do not reverse or slow the disease course but only treat its manifestations. This limitation has brought attention to the need for treatments that modify the amyloid‐beta (Aβ) and tau pathology of the disease. One recent advancement in AD treatment is donanemab, a monoclonal antibody intended to clear Aβ plaques in the brain. It targets pyroglutamyl(3)‐Aβ protein (3–42) to remove Aβ deposits and alter the disease course. This review explores the timeline of donanemab use from discovery to clinical use. The pharmacodynamics and pharmacokinetics of the drug are discussed along with typical and suboptimal preclinical and clinical trial results in terms of efficacy, safety, and tolerability. Thus, donanemab is more effective than donepezil and rivastigmine in removing plaques and improving cognition. At the same time, it is not devoid of safety concerns that are typical of the majority of amyloid‐targeted medicines. The control to end the treatment after plaque cleaning is a unique selling point for some patients, making it more attractive. The innovation and development of donanemab from research to clinical practice are a clear representation of the role of the field of translational medicine in the practical application of new knowledge in the treatment of AD.
C(sp2)−H Acylation of Benzo[h]quinolines at Room Temperature via Aldehyde Autoxidation and Palladium Catalysis Cooperation
Authors: Roy Ishita , Mandal Nilangshu , Biswas Promita , Datta Ayan , Guin Joyram 
Published: December 2024

AbstractHerein, we report Pd‐catalyzed C(sp2)−H acylation using aldehyde as acyl source and O2 as the green oxidant at room temperature. A selective association of acyl radical formed in‐situ during aldehyde autoxidation with Pd‐catalysis is the key to the process. The reaction afforded products in good yields (up to 82 %) and it is scalable. The proposed PdII/PdIII‐catalytic cycle is supported by a series of control studies and DFT calculations.