bluuebunny/crossref_metadata_2025_split huggingface dataset:
Single‐Anion Conductive Solid‐State Electrolytes with Hierarchical Ionic Highways for Flexible Zinc‐Air Battery
Authors: Xu Mi , Cao Rui , Hao Boying , Wang Dongdong , Luo Dan , Dou Haozhen , Chen Zhongwei 
Published: June 2024

AbstractFlexible zinc‐air batteries are leading power sources for next‐generation smart wearable electronics. However, flexible zinc‐air batteries suffer from the highly‐corrosive safety risk and limited lifespan due to the absence of reliable solid‐state electrolytes (SSEs). Herein, a single‐anion conductive SSE with high‐safety is constructed by incorporating a highly amorphous dual‐cation ionomer into a robust hybrid matrix of functional carbon nanotubes and polyacrylamide polymer. The as‐fabricated SSE obtains dual‐penetrating ionomer‐polymer networks and hierarchical ionic highways, which contribute to mechanical robustness with 1200 % stretchability, decent water uptake and retention, and superhigh ion conductivity of 245 mS ⋅ cm−1 and good Zn anode reversibility. Remarkably, the flexible solid‐state zinc‐air batteries delivers a high specific capacity of 764 mAh ⋅ g−1 and peak power density of 152 mW ⋅ cm−2 as well as sustains excellent cycling stability for 1050 cycles (350 hours). This work offers a new paradigm of OH− conductors and broadens the definition and scope of OH− conductors.
Antifouling Asymmetric Block Copolymer Nanofilms via Freestanding Interfacial Polymerization for Efficient and Sustainable Water Purification
Authors: Chen Yu , Song Kaiyuan , Li Ziying , Su Yue , Yu Li , Chen Baiyang , Huang Qijing , Da Lintai , Han Zeguang , Zhou Yongfeng , Zhu Xinyuan , Xu Jia , Dong Ruijiao 
Published: June 2024

AbstractMembrane materials that resist nonspecific or specific adsorption are urgently required in widespread practical applications, such as water purification, food processing, and life sciences. In water purification, inevitable membrane fouling not only limits membrane separation performance, leading to a decline in both permeance and selectivity, but also remarkably increases operation requirements, and augments extra maintenance costs and higher energy consumption. In this work, we report a freestanding interfacial polymerization (IP) fabrication strategy for in situ creation of asymmetric block copolymer (BCP) nanofilms with antifouling properties, greatly outperforming the conventional surface post‐modification approaches. The resultant free‐standing asymmetric BCP nanofilms with highly‐dense, highly‐hydrophilic polyethylene glycol (PEG) brushes on one side, can be readily formed via a typical IP process of a well‐defined double‐hydrophilic BCP composed of a highly‐efficient antifouling PEG block and a membrane‐forming multiamine block. The asymmetric BCP nanofilms have been applied for efficient and sustainable natural water purification, demonstrating extraordinary antifouling capabilities accompanied with superior separation performance far beyond commercial polyamide nanofiltration membranes. The antifouling behaviors of asymmetric BCP nanofilms derived from the combined effect of the hydration layer, electrostatic repulsion and steric hindrance were further elucidated by water flux and fouling resistance in combination with all‐atom molecular dynamics (MD) simulation. This work opens up a new avenue for the large‐scale and low‐cost creation of broad‐spectrum, asymmetric membrane materials with diverse functional “defect‐free” surfaces in real‐world applications.
Poly(N‐Heterocyclic Carbene)‐Capped Alloy and Core‐Shell AuAg Bimetallic Nanoparticles
Authors: Nguyen Diep T. H. , Salek Samaneh , Shultz‐Johnson Lorianne R. , Bélanger‐Bouliga Marilyne , Jurca Titel , Byers Joshua C. , Nazemi Ali 
Published: June 2024

AbstractN‐Heterocyclic carbene (NHC)‐stabilized metal nanoparticles (NPs) have recently attracted considerable attention. While most efforts in the field have been devoted to the development of NHC‐tethered monometallic NPs and enhancing their stabilities under various conditions, their bimetallic counterparts are rare in the literature. Herein, we demonstrate that the covalent immobilization of Au and Ag atoms on polymerized NHCs is a powerful method to access bimetallic AuAg NPs. In addition, we show that while AuAg alloy NPs are often obtained via this method, the use of bimetallic polymeric substrates with lower Ag content, relative to Au, results in the formation of core–shell NPs with Au core and Ag shell. Application of these nanomaterials for oxygen reduction reaction is demonstrated with all materials exhibiting electrocatalytic activity. This work demonstrates for the first time that while bimetallic poly(NHC‐metal)s are viable substrates to access NHC‐stabilized bimetallic NPs, careful adjustment of metal content in the polymeric substrates can finetune the microstructure of the resulting NPs, i.e. alloy vs. core–shell.
Inducing Immunogenic Cancer Cell Death through Oxygen‐Economized Photodynamic Therapy with Nitric Oxide‐Releasing Photosensitizers
Authors: Xu Feijie , Wang Meijun , Dotse Eunice , Chow Kwan T. , Lo Pui‐Chi 
Published: June 2024

AbstractPhotodynamic therapy (PDT) utilizes reactive oxygen species (ROS) for eradication of cancer cells. Its effectiveness is governed by the oxygen content, which is scarce in the hypoxic tumor microenvironment. We report herein two zinc(II) phthalocyanines substituted with two or four nitric oxide (NO)‐releasing moieties, namely ZnPc‐2NO and ZnPc‐4NO, which can suppress the mitochondrial respiration, thereby sparing more intracellular oxygen for PDT. Using HT29 human colorectal adenocarcinoma cells and A549 human lung carcinoma cells, we have demonstrated that both conjugates release NO upon interaction with the intracellular glutathione, which can reduce the cellular oxygen consumption rate and adenosine triphosphate generation and alter the mitochondrial membrane potential. They can also relieve the hypoxic status of cancer cells and decrease the expression of hypoxia‐inducible factor protein HIF‐1α. Upon light irradiation, both conjugates can generate ROS and induce cytotoxicity even under a hypoxic condition, overcoming the oxygen‐dependent nature of PDT. Interestingly, the photodynamic action of ZnPc‐2NO elicits the release of damage‐associated molecular patterns, inducing the maturation of dendritic cells and triggering an antitumor immune response. The immunogenic cell death caused by this oxygen‐economized PDT has been demonstrated through a series of in vitro and in vivo experiments.
Hollow Core‐Shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with Tiny‐Void Space Capable Fast‐Charge and Low‐Temperature Sodium Storage
Authors: Qi Xinran , Dong Hanghang , Yan Hao , Hou Baoxiu , Liu Haiyan , Shang Ningzhao , Wang Longgang , Song Jianjun , Chen Shuangqiang , Chou Shulei , Zhao Xiaoxian 
Published: June 2024

AbstractIron‐based mixed polyanion phosphate Na4Fe3(PO4)2P2O7 (NFPP) is recognized as a promising cathode for Sodium‐ion Batteries (SIBs) due to its low cost and environmental friendliness. However, its inherent low conductivity and sluggish Na+ diffusion limit fast charge and low‐temperature sodium storage. This study pioneers a scalable synthesis of hollow core–shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with tiny‐void space (THoCS‐0.6Ni) via a one‐step spray‐drying combined with calcination process due to the different viscosity, coordination ability, molar ratios, and shrinkage rates between citric acid and polyvinylpyrrolidone. This unique structure with interconnected carbon networks ensures rapid electron transport and fast Na+ diffusion, as well as efficient space utilization for relieving volume expansion. Incorporating regulation of lattice structure by doping Ni heteroatom to effectively improve intrinsic electron conductivity and optimize Na+ diffusion path and energy barrier, which achieves fast charge and low‐temperature sodium storage. As a result, THoCS‐0.6Ni exhibits superior rate capability (86.4 mAh g−1 at 25 C). Notably, THoCS‐0.6Ni demonstrates exceptional cycling stability at −20 °C with a capacity of 43.6 mAh g−1 after 2500 cycles at 5 C. This work provides a universal strategy to design the hollow core–shelled structure with tiny‐void space cathode materials for reversible batteries with fast‐charge and low‐temperature Na‐storage features.
Hierarchical two‐dimensional Ti‐MOF derived from MXene for hybrid supercapacitor electrodes
Authors: Li Sumin , Cheng Qiang , Ye Pingwei , Zhang Yang , Zhang Limin , Liu Feng , Qiu Han , Qu Xiaokun , Nie Yijing 
Published: June 2024

Presently, two‐dimensional (2D) metal–organic framework (MOF) are drawing increasing attention in energy‐storage areas. However, more and complexed factors would affect the nucleation and growth of 2D MOFs, and subsequently affect the final performance. Particularly, it is important to control the coordination rate between ions and ligands. In this paper, MXene was directly used as titanium source to coordinate with an organic ligand to form Ti‐MOF sheets. To further boost the performance, mesopores were introduced in preparing 2D Ti‐MOF, constructing hierarchical porous Ti‐MOF@Ti3C2TX hybrids. Results showed that diffusion‐controlled behaviors play a dominant role over surface capacitive behaviors during the charge storage process of the hierarchical porous hybrids. A hybrid supercapacitor (HSC) assembled with the obtained HP‐Ti‐MOF@Ti3C2TX and activated carbon (AC) exhibited an energy density of 22.9 Wh kg−1 at a power density of 850 W kg−1 (1 A g−1), and a power density of 4.25 kW kg−1 at an energy density of 15.3 Wh kg−1 (5 A g−1). The present strategy is expected to provide design ideas for novel energy‐storage electrode materials.
Sn‐Doped Carbon Black as an Active Conductive Additive for Lithium‐Ion Batteries
Authors: Yang Hyeonsu , Kim Seonghee , Kang Jun , Lun Li Oi 
Published: June 2024

AbstractCarbon black is commonly used as a conductive additive for lithium‐ion battery (LIB) electrodes owing to its high electrical conductivity and cost‐effectiveness. However, the role of traditional conductive additives has been limited to imparting conductivity to the electrode. In this study, we investigate the effect of incorporating Sn nanoparticles, which form an alloy with lithium, into a conductive carbon matrix (Sn@C) for enhancing the lithium storage capacity. This approach combines an active material with a conductive additive and successfully demonstrates the utilization of Sn@C as an “active” conductive additive for LIBs. Sn@C is synthesized via plasma engineering, wherein Sn nanoparticles are uniformly dispersed within a carbon matrix. When Sn@C‐500, Sn@C annealed at 500 °C, is used as an “active” conductive additive in LIB half‐cell with a graphite anode, ~10 % higher reversible capacity than that of a commercial conductive additive (Super P) is achieved. Further, electrochemical impedance spectroscopy studies reveal that Sn@C‐500 exhibits a lower internal resistance than Super P, confirming its effectivity in providing internal conductivity to the electrode. Our results open up the possibilities for improving the performance of graphite anodes in LIBs using Sn‐doped carbon as an active material and conductive additive.
Icaritin exhibits potential drug–drug interactions through the inhibition of human UDP‐glucuronosyltransferase in vitro
Authors: Rong Yi , Li Nanxi , Qiao Xuan , Yang Lei , Han Peng , Meng Zhiyun , Gan Hui , Wu Zhuona , Zhu Xiaoxia , Sun Yunbo , Liu Shuchen , Dou Guifang , Gu Ruolan 
Published: June 2024

AbstractIcaritin is a prenylflavonoid derivative of the genus Epimedium (Berberidaceae) and has a variety of pharmacological actions. Icaritin is approved by the National Medical Products Administration as an anticancer drug that exhibits efficacy and safety advantages in patients with hepatocellular carcinoma cells. This study aimed to evaluate the inhibitory effects of icaritin on UDP‐glucuronosyltransferase (UGT) isoforms. 4‐Methylumbelliferone (4‐MU) was employed as a probe drug for all the tested UGT isoforms using in vitro human liver microsomes (HLM). The inhibition potentials of UGT1A1 and 1A9 in HLM were further tested by employing 17β‐estradiol (E2) and propofol (PRO) as probe substrates, respectively. The results showed that icaritin inhibits UGT1A1, 1A3, 1A4, 1A7, 1A8, 1A10, 2B7, and 2B15. Furthermore, icaritin exhibited a mixed inhibition of UGT1A1, 1A3, and 1A9, and the inhibition kinetic parameters (Ki) were calculated to be 3.538, 2.117, and 0.306 (μM), respectively. The inhibition of human liver microsomal UGT1A1 and 1A9 both followed mixed mechanism, with Ki values of 2.694 and 1.431 (μM). This study provides supporting information for understanding the drug–drug interaction (DDI) potential of the flavonoid icaritin and other UGT‐metabolized drugs in clinical settings. In addition, the findings provide safety evidence for DDI when liver cancer patients receive a combination therapy including icaritin.
Synthesis of 9‐(substituted phenoxycarbonyl)‐10‐methylacridinium trifluoromethanesulfonates: Effects of the leaving group on chemiluminescent properties
Authors: Smith Keith , Holland Andy M. , Woodhead J. Stuart , El‐Hiti Gamal A. 
Published: June 2024

AbstractVarious 9‐(substituted phenoxycarbonyl)‐10‐methylacridinium trifluoromethanesulfonates possessing electron‐withdrawing substituents have been synthesized. The effect of substituents on the stability of the acridinium esters (AEs) at various temperatures in different buffers and the chemiluminescent properties have been examined. There was little correlation between the chemiluminescent properties of AEs and the pKa values of their associated phenols, but the steric effects of the ortho‐substituents in the phenoxy group, as well as their electron‐withdrawing natures, seem to play an important role in determining the properties. In general, when two identical substituents are present in the 2‐ and 6‐positions, the compound is significantly more stable than when only a single substituent is present, presumably because of greater steric hindrance from the second group. The exception is the 2,6‐difluorophenyl ester, which is less stable than the 2‐fluorophenyl ester, presumably because the fluoro group is small. Addition of a third electron‐withdrawing substituent at the 4‐position, where it has no steric influence, typically increases susceptibility to decomposition. The presence of a nitro group has a significant destabilizing effect on AEs. Of the AEs studied, the 4‐chlorophenyl ester showed the greatest chemiluminescent yield, while the 2‐iodo‐6‐(trifluoromethyl)phenyl ester group showed the greatest stability in low pH buffers.
Effects of Chemical Modification on the Structure and Biological Activities of Polysaccharides Extracted from Inonotus Obliquus by Microwave
Authors: Xie Hao , Li Wenwen , Zhang Linghe , Eliyas Nurmamat 
Published: June 2024

AbstractA novel polysaccharide, Inonotus obliquus polysaccharide (IOP), was extracted using a microwave extraction method and subsequently subjected to modifications through sulfation, carboxymethylation, phosphorylation, and acetylation. Its physical and chemical properties were analyzed using various chemical techniques, including high‐pressure liquid chromatography, ultraviolet light, Fourier‐transform infrared spectroscopy, X‐ray diffraction, Congo red test, and scanning electron microscopy. The antioxidant capacity was assessed using DPPH, ABTS, and hydroxyl radical assays, as well as by measuring the reducing power. Additionally, hypoglycemic activity was evaluated through α‐glucosidase and α‐amylase assays. The results indicated that the chemical modifications effectively altered the physical and chemical properties, as well as the biological activities of IOP. Compared to the unmodified IOP, the derivatives exhibited reduced sugar content, uronic acid content, and molecular weight, while demonstrating varying levels of antioxidant and hypoglycemic capabilities. Notably, the carboxymethylated IOP (IOP−C) displayed lower molecular weight, higher ABTS free radical scavenging rate, greater reducing ability, and increased α‐amylase inhibition rate. Therefore, IOP−C shows promise as a potential edible antioxidant and hypoglycemic agent.
GSE1 promotes the proliferation and migration of lung adenocarcinoma cells by downregulating KLF6 expression
Authors: Meng Ziyu , Yang Yingqian , Li Shupei , Huang Liguo , Yao Zhoujuan , Chen Yixuan , Wang Junkun , Shen Yiru , Liang Pingping , Zhang Hui , Wang Wenbin , Wang Fengsong 
Published: June 2024

AbstractLung cancer is one of the most prevalent human cancers with a high lethality rate worldwide. In this study, we demonstrated that GSE1 (genetic suppressor element 1) expression is aberrantly upregulated in lung adenocarcinoma and that GSE1 depletion inhibits the proliferation and migration of both A549 and H1299 cells. Immunoprecipitation assays demonstrated that GSE1 interacts with histone deacetylase 1 (HDAC1) and other BRAF–HDAC complex (BHC) components in cells. The transcriptome of GSE1‐knockdown A549 cells indicated that 207 genes were upregulated and 159 were downregulated based on a p‐value < .05 and fold change ≥ 1.5. Bioinformatics analysis suggested that 140 differentially expressed genes harbor binding sites for HDAC1, including the tumor suppressor gene KLF6 (Kruppel‐like factor 6). Indeed, quantitative reverse‐transcription polymerase chain reaction and western blot analysis revealed that GSE1 could inhibit the transcription of KLF6 in lung cancer cells. In conclusion, GSE1 cooperates with HDAC1 to promote the proliferation and metastasis of non‐small cell lung cancer cells through the downregulation of KLF6 expression.
Tunable Catalytic Reduction of Furfural with Formic Acid and Sodium Formate Into Furan and Tetrahydrofuran Derivatives
Authors: Oksanen Valtteri , van Strien Nicolaas , Viertiö Tyko , Vuorio Niko , Gauli Bibesh , Helosuo Kirsti , Meriläinen Veronika , Myllykylä Emmi , Rautiainen Sari , Wirtanen Tom 
Published: June 2024

AbstractFurfural is an attractive bio‐based platform chemical that has many derivatives of commercial interest. Herein, we show that the selectivity of the direct furfural reduction can be steered from 2‐methylfuran and 2‐methyltetrahydrofuran to furfuryl alcohol and tetrahydrofurfuryl alcohol by varying the ratio of formic acid and sodium formate. These reagents take the role of terminal reductants in the disclosed heterogeneous Pd‐catalysed process. We report the development and optimisation of the reaction conditions for three different products directly from furfural: 2‐methyltetrahydrofuran, tetrahydrofurfuryl alcohol and 2‐methylfuran which were obtained in 59 %, 46 %, and 63 % selectivity, respectively. Furthermore, the protocol uses commercially available Pd/Al2O3 as catalyst and the formic acid and sodium formate can be obtained from biogenous sources.
SPOs as Non‐Innocent Ligands in Chiral‐at‐Iridium Catalyzed Asymmetric Hydrogenations
Authors: Pazos Ariadna , Freixa Zoraida 
Published: June 2024

AbstractA series of bis‐cyclometalated chiral‐at‐metal iridium(III) complexes containing a coordinated secondary phosphine oxide (SPO) have been synthesized and evaluated as catalysts in the asymmetric transfer hydrogenation (ATH) of acetophenone. The catalytic results show that SPO ligands have a non‐innocent role in activating the catalytic process. Additionally, it has been observed that for the same chiral descriptor (Δ‐at‐Ir or Λ‐at‐Ir), the major enantiomer formed depends on the nature of the cyclometalating ligand. These enantiodivergent results contravene the general assumption that the chiral‐at‐metal core‘s chirality dictates the sense of the chiral induction. A combined analysis of the main structural features of the catalysts deduced from XRD structures and in situ NMR spectroscopy allowed us to propose a simplified catalytic cycle and a working hypothesis to explain the observed enantioselectivities.
Theoretical Studies on the Catalytic Mechanism and Cyclization Pattern of Fungal Polyketide Synthase Product Template Domain
Authors: Ji Huining , Shi Ting , Zhao Yi‐Lei , Zheng Jianting 
Published: June 2024

AbstractAromatic polyketides are pharmaceutically significant natural products. Product template (PT) domains from fungal non‐reducing polyketide synthases (NR‐PKSs) control the regioselective aldol cyclization of highly reactive polyketide intermediates, whose instabilities have hindered experimental studies. The molecular basis of PT‐catalyzed cyclization and aromatization remain ambiguous. Herein, we conducted MD simulations and QM/MM calculations to explore the catalytic mechanHism and the cyclization pattern of PksA PT specific for C4−C9. The cyclization mediated by PksA PT is initiated by the C4 deprotonation followed by the aldol condensation in C4−C9 register. PTs which evolve from ancient PKS dehydratases (DHs) perform dehydration reactions to aromatize the cyclized intermediates. In PksA PT, the catalytic His1345 and Asp1543 are responsible for aldol cyclization and aromatization steps, respectively. A keto‐enol tautomerism at C3 assists in the elimination reaction catalyzed by Asp1543 with a water molecule network, different from most DHs of PKSs. The C2−C7 aldol cyclization in PksA PT can occur, but the subsequent dehydration step is kinetically unfeasible and thermodynamically unfavorable, suggesting that the aromatization steps determine the C4−C9 cyclization mode of PksA PT. Overall, these computational investigations provide detailed mechanistic insights into the regiospecific intramolecular cyclization and aromatization controlled by fungal PksA PT.
Rational Design of Photoanodes to Produce Value‐Added Chemicals Coupled with Hydrogen
Authors: Khan Hasmat , Bera Susanta , Jung Myung‐Jin , Kwon Se‐Hun 
Published: June 2024

AbstractGreen hydrogen fuel generation via the photoelectrochemical (PEC) approach has attracted considerable attention recently for its sustainability and eco‐friendliness. Photoelectrocatalysts are the key component of the PEC process. To produce green hydrogen by this approach at a reasonable rate from water splitting and waste valorization, proper design and electronic structure modulation of the photoelectrocatalysts are of utmost importance. Therefore, in this review, we discuss the materials selection, design, and engineering of photoanode materials to efficiently harvest and convert solar energy into green hydrogen fuel and value‐added chemicals. In this regard, we introduce the fundamentals and the mechanistic insights of the PEC solar energy conversion and storage technologies, which would provide knowledge to novices to gain insight into this field while designing a new photoanode. Moreover, we mention the importance of various semiconducting materials and their surface/interface engineering aspects to improve the PEC properties for selective water oxidation to value‐added chemicals and waste valorization coupled with green hydrogen generation. Finally, we discuss the conclusions and prospects of this technology by highlighting the major challenges and its potential for commercialization.
Organic Reactions Enabled by Mechanical Force‐Induced Single Electron Transfer
Authors: Liu Ruoxuan , He Xiaochun , Liu Tianfen , Wang Xiaohong , Wang Qingqing , Chen Xinzhou , Lian Zhong 
Published: June 2024

AbstractMechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent‐free alternative to traditional solution‐based chemistry. Mechanochemistry not only provides the opportunity to eliminate bulk solvent use, reducing waste generation, but also unveils a new reaction strategy which enables the realization of reactions previously inaccessible in solution. While the majority of organic reactions facilitated by mechanical force traditionally follow two‐electron transfer pathways similar to their solution‐based counterparts, the field of mechanochemically induced single‐electron transfer (SET) reactions has witnessed rapid development. This review outlines examples of mechanochemical reactions facilitated by the SET process, focusing on the reagents that initiate SET, thereby positioning mechanochemistry as a burgeoning field within the realm of single‐electron chemistry.