bluuebunny/crossref_metadata_2025_split huggingface dataset:
DMSO/SOCl2‐Mediated Synthesis of Thiomethylnaphthalenes from Propargyl Alcohols
Authors: Wang Zhihua , Liang Wang‐Fu , He Xinglei , Li Jingheng , Ye Ke‐Yin 
Published: October 2024

AbstractHerein, we reported the straightforward synthesis of thiomethylnaphthalenes via the reaction of propargyl alcohols with dimethyl sulfoxide/thionyl chloride (DMSO/SOCl2), which also provided easy access to deuterated thiomethyl and other thioalkyl scaffolds when deuterated dimethyl sulfoxide and dialkyl sulfoxides were used, respectively. In addition, the thiomethyl group can be readily derivatized to the corresponding sulfoxide, sulfone, and sulfoximine of interesting photophysical properties.
Selective Modulation of Fear Memory in Non‐Rapid Eye Movement Sleep
Authors: Zheng Qiyu , Huang Yuhua , Mu Changrui , Hu Xiaoqing , Lai Cora Sau Wan 
Published: October 2024

AbstractSleep stabilizes memories for their consolidation, but how to modify specific fear memory during sleep remains unclear. Here, it is reported that using targeted memory reactivation (TMR) to reactivate prior fear learning experience in non‐slow wave sleep (NS) inhibits fear memory consolidation, while TMR during slow wave sleep (SWS) enhances fear memory in mice. Replaying conditioned stimulus (CS) during sleep affects sleep spindle occurrence, leading to the reduction or enhancement of slow oscillation‐spindle (SO‐spindle) coupling in NS and SWS, respectively. Optogenetic inhibition of pyramidal neurons in the frontal association cortex (FrA) during TMR abolishes the behavioral effects of NS‐TMR and SWS‐TMR by modulating SO‐spindle coupling. Notably, calcium imaging of the L2/3 pyramidal neurons in the FrA shows that CS during SWS selectively enhances the activity of neurons previously activated during fear conditioning (FC+ neurons), which significantly correlates with CS‐elicited spindle power spectrum density. Intriguingly, these TMR‐induced calcium activity changes of FC+ neurons further correlate with mice freezing behavior, suggesting their contributions to the consolidation of fear memories. The findings indicate that TMR can selectively weaken or strengthen fear memory, in correlation with modulating SO‐spindle coupling and the reactivation of FC+ neurons during substages of non‐rapid eye movement (NREM) sleep.
Specific Requirement of the p84/p110γ Complex of PI3Kγ for Antibody‐Activated, Inducible Cross‐Presentation in Murine Type 2 DCs
Authors: Koumantou Despoina , Adiko Aimé Cézaire , Bourdely Pierre , Nugue Mathilde , Boedec Erwan , El‐Benna Jamel , Monteiro Renato , Saveanu Cosmin , Laffargue Muriel , Wymann Matthias P. , Dalod Marc , Guermonprez Pierre , Saveanu Loredana 
Published: October 2024

AbstractCross‐presentation by MHCI is optimally efficient in type 1 dendritic cells (DC) due to their high capacity for antigen processing. However, through specific pathways, other DCs, such as type 2 DCs and inflammatory DCs (iDCs) can also cross‐present antigens. FcγR‐mediated uptake by type 2 DC and iDC subsets mediates antibody‐dependent cross‐presentation and activation of CD8+ T cell responses. Here, an important role for the p84 regulatory subunit of PI3Kγ in mediating efficient cross‐presentation of exogenous antigens in otherwise inefficient cross‐presenting cells, such as type 2 DCs and GM‐CSF‐derived iDCs is identified. FcγR‐mediated cross‐presentation is shown in type 2 and iDCs depend on the enzymatic activity of the p84/p110γ complex of PI3Kγ, which controls the activity of the NADPH oxidase NOX2 and ROS production in murine spleen type 2 DCs and GM‐CSF‐derived iDCs. In contrast, p84/p110γ is largely dispensable for cross‐presentation by type 1 DCs. These findings suggest that PI3Kγ‐targeted therapies, currently considered for oncological practice, may interfere with the ability of type 2 DCs and iDCs to cross‐present antigens contained in immune complexes.
Photocatalytic Hydrogenation of Alkenes Using Water as Both the Reductant and the Proton Source
Authors: Tian Xinzhe , Qiu Ming , An Wankai , Ren Yun‐Lai 
Published: October 2024

AbstractUtilization of clean and low‐cost water as the reductant to enable hydrogenation of alkenes is highly attractive in green chemistry. However, this research subject is considerably challenging due to the sluggish kinetics of the water oxidation half‐reaction. It is also very difficult to avoid the undesired oxidation of alkenes because that this oxidation is far easier to occur than the desired oxidation of water from thermodynamic standpoint. Herein, this challenge is overcome by applying a cooperative catalysis where HCl is used as the cocatalyst to accelerate Pt/g‐C3N4‐catalyzed water oxidation and suppress the undesired oxidation of the alkene. This provides an example for using water as the reductant and the proton source to enable the photocatalytic hydrogenation of alkenes. The present method exhibits broad substrate applicability, and allows various arylethenes and aliphatic alkenes to undergo the hydrogenation smoothly.
Manipulating d‐Band Center of Ru Sites in Branched RuO2 Nanofibers Enables Significantly Enhanced Alkaline Overall Water Splitting Performance
Authors: Zhang Linfeng , Li Weimo , Ren Siyu , Song Wei , Wang Ce , Lu Xiaofeng 
Published: October 2024

AbstractAlthough ruthenium dioxide (RuO2) is an efficacious oxygen evolution reaction (OER) catalyst in acidic media, its performance in alkaline conditions is subpar and it is also ineffective for hydrogen evolution reaction (HER) in common electrolytes. Here, an effective phosphorus (P)‐doping strategy is introduced to manipulate the d‐band center of ruthenium (Ru) sites, attenuating the adsorption energy of HER intermediates and lowering the energy barrier in OER, thereby significantly accelerating both HER and OER performance. The representative 10%P‐RuO2 nanofibers (NFs) catalyst presents an ultralow overpotential of 177.9 mV at 1 A cm−2 and long‐term stability of 300 h in 1 m KOH toward HER, greatly exceeding those of benchmark platinum (Pt)/C catalyst. Moreover, the 10%P‐RuO2 NFs catalyst exhibits an exceptional OER performance with a low overpotential of 250 mV at 10 mA cm−2 (η10) and desirable stability of 150 h at 1 A cm−2, which is far better than commercial RuO2 and many other typical previously reported OER catalysts. Additionally, an overall water electrolytic cell using 10%P‐RuO2 NFs as both anode and cathode necessitates a working voltage of 1.52 V (η10) and demonstrates long‐term stability over 100 h at 1 A cm−2, outperforming many typical water electrolysis cells.
Directional Electron Transfer in Enzymatic Nano‐Bio Hybrids for Selective Photobiocatalytic Conversion of Nitrate
Authors: Bian Jiyong , An Xiaoqiang , Zhao Jing , Liao Yang , Lan Xianen , Liu Ruiping , Hu Chengzhi , Chen Jie‐jie , Liu Huijuan , Qu Jiuhui 
Published: October 2024

AbstractSemi‐artificial photosynthetic system (SAPS) that combines enzymes or cellular organisms with light‐absorbing semiconductors, has emerged as an attractive approach for nitrogen conversion, yet faces the challenge of reaction pathway regulation. Herein, we find that photoelectrons can transfer from the −C≡N groups at the edge of cyano‐rich carbon nitride (g‐C3N4‐CN) to nitrate reductase (NarGH), while the direct electron transfer to nitrite reductase (cd1NiR) is inhibited due to the physiological distance limit of active sites (>14 Å). By means of the directional electron transfer between g‐C3N4‐CN and extracted biological enzymes, the product of the denitrification reaction was switched from inert N2 to usable nitrite with an unprecedented selectivity of up to 95.3 %. The converted nitrite could be further utilized by anammox microbiota and dissimilatory nitrate reduction to ammonia (DNRA) microorganisms, doubling the efficiency of total nitrogen removal (96.5±2.3 %) for biological nitrogen removal and ammonia generation (12.6 mg NH4+‐N L−1 h−1), respectively. Thus, our work paves an appealing way for the sustainable treatment and utilization of nitrate for ammonia fuel production by strategically regulating the electron transfer pathway across the biotic‐abiotic interface.
Establishing a Robust Nonlinear Targeted Switch for C1 Electroproduction in Atomic Alloy Cox/Pd Bimetallenes
Authors: Pei Jiajing , Li Can , Zhang Guikai , Liao Jiangwen , Yu Yue , Wang Ruqi , Wang Ping , Li Ang , An Pengfei , Chu Shengqi , Dong Juncai 
Published: October 2024

AbstractEstablishing a targeted switch for CO2 conversion under electric drive is essential for achieving carbon‐balance by enabling selective chemicals. However, engineering the topological assembly of active sites to precisely regulate the competing pathways for various intermediates has been plagued by unclear structure‐function relationships. To tailor the CO/formate pathways, herein we established a robust nonlinear targeted switch with tunable active Cox sites integrated into Pd metallene, which involves Co1/Pd single‐atom alloy (favoring CO) and Co2/Pd diatomic alloy (favoring formate). Transitioning from Co1/Pd to Co2/Pd atomic alloy bimetallenes resulted in a nonlinear, high‐contrast flip in selectivity, surpassing 94 % for CO and formate productions in both H‐cell and flow cell. Furthermore, the superior selectivity and current efficiency for CO (>80 %) and formate (>88 %) were consistently maintained at −150 mA cm−2 over continuous 200 h. Theoretical simulations and in situ spectroscopy analyses unveiled that appropriate adjacent metal site combinations (Pd−Pd, Pd−Co and Co−Co) lead to tunable dz2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C1 pathways. Our finding reveals a desired switch in C1 selectivity and robust stability within Cox/Pd system, providing a new perspective for fine‐tuning energy conversion processes through specific topological assembly.
Switchable Topologically Chiral [2]Catenane as Multiple Resonance Thermally Activated Delayed Fluorescence Emitter for Efficient Circularly Polarized Electroluminescence
Authors: Wang Yu , Zhao Wen‐Long , Gao Zhiwen , Qu Cheng , Li Xue , Jiang Yefei , Hu Lianrui , Wang Xu‐Qing , Li Meng , Wang Wei , Chen Chuan‐Feng , Yang Hai‐Bo 
Published: October 2024

AbstractAiming at the fabrication of circularly polarized organic light‐emitting diodes (CP‐OLEDs) with high dissymmetry factors (gEL) and color purity through the employment of novel chiral source, topologically chiral [2]catenanes were first utilized as the key chiral skeleton to construct novel multi‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters. Impressively, the efficient chirality induction and unique switchable feature of topologically chiral [2]catenane not only lead to a high |gPL| value up to 1.6×10−2 but also facilitate in situ dynamic switching of the full‐width at half‐maximum (FWHM) and circularly polarized luminescence (CPL). Furthermore, the solution‐processed CP‐OLEDs based on the resultant topologically chiral emitters exhibit a narrow FWHM of 36 nm, maximum external quantum efficiency of 17.6 %, and CPEL with |gEL| of 2.1×10−3. This study demonstrates the successful construction of the first CP‐MR‐TADF emitters based on topological chirality with the highest |gPL| among the reported CP‐MR‐TADF emitters and excellent device performance to the best of our knowledge. Moreover, it endowed the MR‐TADF emitter with distinctive switchable CPL performances, thus providing a novel design strategy as well as a promising platform for developing intelligent CP‐OLEDs.
Visible‐Light‐Driven Oxidation of Benzene to Phenol with O2 over Photoinduced Oxygen‐Vacancy‐Rich WO3
Authors: Zhou Wenhui , Wang Xiaoyi , Lin Feng , Xue Sikang , Lin Wei , Hou Yidong , Yu Zhiyang , Anpo Masakazu , Yu Jimmy C. , Zhang Jinshui , Wang Xinchen 
Published: October 2024

AbstractDirect photocatalytic conversion of benzene to phenol with molecular oxygen (O2) is a green alternative to the traditional synthesis. The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O2 activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO3) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O2 as they readily capture photogenerated electrons from the reductive sites of WO3 to activate adsorbed O2. The oxygen‐isotope‐labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O2 into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high‐performance OVs‐rich photocatalysts for solar‐induced chemical conversion.
Piperazine‐Derived Bisphosphonate‐Based Ionizable Lipid Nanoparticles Enhance mRNA Delivery to the Bone Microenvironment
Authors: Yoon Il‐Chul , Xue Lulu , Chen Qinyuan , Liu Jingyi , Xu Junchao , Siddiqui Zain , Kim Dongyoon , Chen Bingling , Shi Qiangqiang , Laura Han Emily , Cherry Ruiz Mia , Vining Kyle H. , Mitchell Michael J. 
Published: October 2024

AbstractNucleic acid delivery with mRNA lipid nanoparticles are being developed for targeting a wide array of tissues and cell types. However, targeted delivery to the bone microenvironment remains a significant challenge in the field, due in part to low local blood flow and poor interactions between drug carriers and bone material. Here we report bone‐targeting ionizable lipids incorporating a piperazine backbone and bisphosphate moieties, which bind tightly with hydroxyapatite ([Ca5(PO4)3OH]), a key component of mineralized tissues. These lipids demonstrate biocompatibility and low toxicity in both vitro and in vivo studies. LNP formulated with these lipids facilitated efficient cellular transfection and improved binding to hydroxyapatite in vitro, and targeted delivery to the bone microenvironment in vivo following systemic administration. Overall, our findings demonstrate the critical role of the piperazine backbone in a novel ionizable lipid, which incorporates a bisphosphonate group to enable efficient bone‐targeted delivery, highlighting the potential of rational design of ionizable lipids for next‐generation bone‐targeting delivery systems.
Ultra‐Efficient Heat Transport Across a “2.5D” All‐Carbon sp2/sp3 Hybrid Interface
Authors: Qiu Lin , Li Haimo , Yuan Xiaolu , Li Fengcheng , Feng Yanhui , Li Chengming , Liu Jinlong , Zhang Xiaohua 
Published: October 2024

AbstractSingle‐ and few‐layer graphene‐based thermal interface materials (TIMs) with extraordinary high‐temperature resistance and ultra‐high thermal conductivity are very essential to develop the next‐generation integrated circuits. However, the function of the as‐prepared graphene‐based TIMs would undergo severe degradation when being transferred to chips, as the interface between the TIMs and chips possesses a very small interfacial thermal conductance. Here, a “2.5D” all‐carbon interface containing rich covalent bonding, namely a sp2/sp3 hybrid interfaces is designed and realized by a plasma‐assisted chemical vapor deposition with a function of ultra‐rapid quenching. The interfacial thermal conductance of the 2.5D interface is excitingly very high, up to 110–117 MWm−2 K−1 at graphene thickness of 12–25 nm, which is even more than 30 % higher than various metal/diamond contacts, and orders of magnitude higher than the existing all‐carbon contacts. Atomic‐level simulation confirm the key role of the efficient heat conduction via covalent C−C bonds, and reveal that the covalent‐based heat transport could contribute 85 % to the total interfacial conduction at a hybridization degree of 22 at %. This study provides an efficient strategy to design and construct 2.5D all‐carbon interfaces, which can be used to develop high performance all‐carbon devices and circuits.
Regulating Intermolecular Hydrogen Bonds in Organic Cathode Materials to Realize Ultra‐stable, Flexible and Low‐temperature Aqueous Zinc‐organic Batteries
Authors: Ding Chaojian , Zhao Yuxuan , Yin Weifeng , Kang Fangyuan , Huang Weiwei , Zhang Qichun 
Published: October 2024

AbstractRational design of molecular structures is one of the effective strategies to obtain high‐performance organic cathode materials. However, besides the optimization of single‐molecule structures, the influence of the “weak” interaction forces (e.g. hydrogen bonds) in organic cathode materials on the performance of batteries should be fully considered. Herein, three organic small molecules with different numbers of hydroxyl groups (namely nitrogen heterocyclic tetraketone (DAB), monohydroxyl nitrogen heterocyclic dione (HDA), dihydroxyl nitrogen heterocyclic dione (DHT)) were selected as the cathodes of aqueous zinc ion batteries (AZIBs), and the effect of the intermolecular hydrogen bonds on their electrochemical performance was studied for the first time. Clearly, the stable hydrogen‐bond networks built through the hydroxyl groups significantly enhance the cycle stability of organic small‐molecule cathodes and facilitate rapid proton conduction between the hydrogen‐bond networks through the Grotthuss mechanism, thereby endowing them with excellent rate performance. In addition, a larger and more dense two‐dimensional hydrogen‐bond network can be constructed through multiple hydroxyl groups, further enhancing the structural stability of organic small‐molecule cathodes, giving them better cycle tolerance, excellent rate performance, and extreme environmental tolerance.
An Experimental Mice Model for Ovalbumin‐Induced Allergic Rhinitis Imbued With Copper Oxide Green Nanoparticles From Leaf Extract of Laurus nobilis
Authors: Liu Tao , Zhou Changming , Gao Ying , Du Xi 
Published: October 2024

ABSTRACTThis study aims to develop a safer and more effective treatment for allergic rhinitis using green‐synthesized copper oxide nanoparticles (CuO NPs) derived from Laurus nobilis (L. nobilis), addressing the limitations of current therapies. The environmentally friendly CuO NPs were evaluated for their antiallergic, anti‐inflammatory, and antimicrobial properties. Various analytical techniques confirmed the successful synthesis of CuO NPs. Phytoconstituents were identified using GC–MS, and molecular docking studies indicated that eugenol and 1H‐cyclopropazulen‐7‐ol, present in L. nobilis leaf extract, could be potential therapeutics targeting the FGFR2 protein. The antibacterial activity of CuO NPs was significant against Gram‐positive (Bacillus subtilis [B. subtilis] and Staphylococcus aureus [S. aureus]) and Gram‐negative (Escherichia coli [E. coli] and Klebsiella pneumoniae [K. pneumoniae]) bacterial strains. In a mouse model, the antiallergic effects were demonstrated by a significant reduction in symptoms like rubbing and sneezing and a decrease in inflammatory cell counts and mediators, including neutrophils, eosinophils, macrophages, lymphocytes, RORc, IL‐17A, IL‐5, IL‐13, and IL‐6. The preclinical results suggest that CuO NPs possess promising antibacterial, antiallergenic, and anti‐inflammatory properties.
Half‐Sandwich Iron Chalcogenopropargylcarbonato Complexes as CO‐Releasing Molecules
Authors: Al‐Shboul Tareq M. A. , El‐khateeb Mohammad , Jazzazi Taghreed M. A. , Quraan Lama , Alsabah Diana , Yasaka Soichiro , Yoshida Yukihiro , Kitagawa Hiroshi 
Published: October 2024

ABSTRACTInteraction of iron chalcogenides (μ‐Ex)[CpFe(CO)2]2 (E = S; x = 2–4, E = Se, x = 1) with propargyl chloroformate (ClCO2CH2C≡CH) in diethyl ether yielded iron(II) chalcogenopropargylcarbonato complexes CpFe(CO)2ECO2CH2C≡CH (E = S (1), Se (2)). These complexes have been characterized by elemental analysis, UV–Vis, IR, and 1H‐ and 13C{1H}‐NMR spectroscopy and single‐crystal x‐ray diffraction techniques. Further, the suitability of complexes 1 and 2 as CO‐releasing molecules (CORMs) for the administration of carbon monoxide has been studied. CO gas is released upon irradiation of THF solution of these complexes in the presence of hemoglobin.
A biodegradable bi‐layer nano fibrous membrane fabricated by centrifugal spinning for active food packaging
Authors: Chen Dongchen , Li Yan , Li Jinzhe , Wang Yaru , Ye Hao , Zhao Mengyao , Li Wanjing , Yang Bin , Li Xianglong 
Published: October 2024

AbstractTo solve the problem of cytotoxicity for most antimicrobial agents loaded in packaging materials, we developed a novel bi‐layer fibrous membrane by using centrifugal spinning, which of the outer layer was submicron native potato starch/polyvinyl alcohol (ST/PVA) composite fibers loaded with ZnO nanoparticles (ZnO NPs) for providing high antibacterial activity. The inner layer was nano‐based calcium alginate/polyethylene oxide (CA/PEO) fiber for providing excellent biocompatibility. The addition of ZnO caused the semicrystalline structures of ST/PVA fibers, while the CA/PEO fibers were shown semicrystalline structures due to the PEO. Fourier transform infrared indicated that posttreatment had not effect on the structures of ST/PVA/ZnO fiber, but the structure of CA/PEO fibers were affected by interaction between COO groups of alginate and Ca2+ ions. The results of mechanical property demonstrated that CA/PEO fibers showed highest stress of 3.83 ± 0.25 MPa and helpful for improving the stress of bi‐layer fibrous membrane. The obtained fibrous membrane had excellent antibacterial property with diameters of bacteriostatic zone against E. coli and S. aureus of 20.5 and 21.5 mm, respectively. On this basis, the shelf life of strawberry was improved up to 6th day by inhibit the growth of microorganisms, which indicated that the obtained fibrous membrane showed great potential for food packaging.
One‐Step Electrodeposition of Iron Oxyhydroxide Onto 3D Porous Graphene Substrates for on Chip Asymmetric Micro‐Supercapacitors
Authors: Braga Filipe , Casano Gabriel , Sonni Manel , Finch Harry , Dhanak Vinod R. , Caffio Marco , Hardwick Laurence J. 
Published: October 2024

AbstractElectrochemical capacitors based on redox active materials can achieve greater capacitance values than traditional electric double layer composites. Herein, electrodeposition of iron oxyhydroxide from a mildly acidic acetate precursor is reported. The one‐step deposition resulted in a submicron film composed of FeOOH phase, which was confirmed via Raman and x‐ray photoelectron spectroscopy. The capacitance increased linearly with loading amount and achieved a maximum at 1600 mC deposition with 120 mF cm−2 at 25 mV s−1 after which the film became more resistive, limiting electrolyte access to the porous graphene substrate. The deposited FeOOH demonstrated promising rate capability and good cycling stability, without phase changes, retaining 82 % of the initial capacitance after 5000 consecutive charge/discharge cycles. The charge storage mechanism of FeOOH was determined via in situ Raman spectroscopy, which followed reversible iron oxygen vibration changes upon cycling which become more intense upon reduction as a result of sodium ion intercalation. Furthermore, an asymmetric configuration full cell combining FeOOH/MnO2 allowed the working voltage to be extended to 2 V, maintaining an ideal capacitor behaviour, and achieving a maximum energy and power density of 21 μWh cm−2 and 2.5 mW cm−2 respectively.