bluuebunny/crossref_metadata_2025_split huggingface dataset:
MBG/BSA Bone Grafts Immunomodulate Bone Regeneration by Releasing Bioactive Ions in Inflammatory Bone Defects
Authors: Yang Yijie , Gu Wen , Jiang Xue , Lv Xiaolei , Wei Jianxu , Zhang Xiaomeng , Zheng Kai , Lai Hongchang 
Published: November 2024

AbstractSince the diseases that cause bone defects are mostly inflammatory diseases, the current bone grafts are unable to effectively regulate osteoimmune activity, leading to the impaired osteogenesis and unfavorable bone regeneration. In this study, inspired by bone composition, biomimetic mesoporous bioactive glass nanoparticle (MBG)/bovine serum albumin (BSA) bone grafts are designed for inflammatory bone defects. Systematically, MBG/BSA bone grafts are evaluated for characterization, bioactivity, anti‐inflammatory, antioxidant activity, and osteogenic activity. MBG/BSA bone grafts are proved to be biocompatible and can release bioactive ions including calcium and silicon in a sustained manner. Furthermore, MBG/BSA reprograms the macrophage phenotype toward anti‐inflammation that is beneficial for bone regeneration. The antioxidative activity is also validated under inflammation and the mechanism may be via the interleukin‐4 (IL‐4)/Signal transducer and activator of transcription 6 (STAT6) pathway. The osteogenic differentiation and mineralization are also facilitated due to the improved immunoregulation of MBG/BSA. Overall, this work suggests that the MBG/BSA bone grafts with improved immunomodulatory properties are an ideal material for inflammatory bone regeneration application.
Incorporating Hydrogel (with Low Polymeric Content) into 3D‐Printed PLGA Scaffolds for Local and Sustained Release of BMP2 in Repairing Large Segmental Bone Defects
Authors: Dong Rongpeng , Kang Mingyang , Qu Yang , Hou Tingting , Zhao Jianwu , Cheng Xueliang 
Published: November 2024

AbstractTreating large bone defects remains a considerable challenge for clinicians: bone repair requires scaffolds with mechanical properties and bioactivities. Herein, based on crosslinking o‐phthalaldehyde (OPA) with amine groups, 4‐arm polyethylene glycol (4armPEG)‐OPA/Gelatin hydrogel loaded with bone morphogenetic protein 2 (BMP2) is prepared and a three dimensional (3D)‐printed poly (lactic‐co‐glycolic acid) (PLGA) porous scaffold is filled with the hydrogel solution. The composite scaffold, with a compression modulus of 0.68 ± 0.097 GPa similar to the cancellous bone, has a porosity of 56.67 ± 4.72% and a pore size of about 380 µm, promoting bone growth. The hydrogel forms a porous network at low concentrations, aiding protein release and cell migration. The hydrogel degrades in approximately three weeks, and the scaffold takes five months, matching bone repair timelines. BMP2 release experiment shows a sustained BMP2 release with a 72.4 ± 0.53% release ratio. The ALP activity test and alizarin red staining shows effective osteogenic promotion, while RT‐PCR confirms BMP2@Gel enhanced COL‐1 and OPN expression. Animal experiments further validate the composite scaffold's bone repair efficacy. This study demonstrates the effectiveness of the hydrogel in releasing BMP2 and the mechanical support of the 3D‐printed PLGA porous scaffold, providing a new treatment for bone defects.
Oxygen Vacancy‐Electron Polarons Featured InSnRuO2 Oxides: Orderly and Concerted In‐Ov‐Ru‐O‐Sn Substructures for Acidic Water Oxidation
Authors: Sun Yanhui , Xiao Mingyue , Liu Feng , Gan Jun , Gao Shixin , Liu Jingjun 
Published: November 2024

AbstractPolymetallic oxides with extraordinary electrons/geometry structure ensembles, trimmed electron bands, and way‐out coordination environments, built by an isomorphic substitution strategy, may create unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, well‐defined rutile InSnRuO2 oxides with density‐controllable oxygen vacancy (Ov)‐free electron polarons are firstly fabricated by in situ isomorphic substitution, using trivalent In species as Ov generators and the adjacent metal ions as electron donors to form orderly and concerted In‐Ov‐Ru‐O‐Sn substructures in the tetravalent oxides. For acidic water oxidation, the obtained InSnRuO2 displays an ultralow overpotential of 183 mV (versus RHE) and a mass activity (MA) of 103.02 A mgRu−1, respectively. For a long‐term stability test of PEMWE, it can run at a low and unchangeable cell potential (1.56 V) for 200 h at 50 mA cm−2, far exceeding current IrO2||Pt/C assembly in 0.5 m H2SO4. Accelerated degradation testing results of PEMWE with pure water as the electrolyte show no significant increase in voltage even when the voltage is gradually increased from 1 to 5 A cm−2. The remarkably improved performance is associated with the concerted In‐Ov‐Ru‐O‐Sn substructures stabilized by the dense Ov‐electron polarons, which synergistically activates band structure of oxygen species and adjacent Ru sites and then boosting the oxygen evolution kinetics. More importantly, the self‐trapped Ov‐electron polaron induces a decrease in the entropy and enthalpy, and efficiently hinder Ru atoms leaching by increasing the lattice atom diffusion energy barrier, achieves long‐term stability of the oxide. This work may open a door to design next‐generation Ru‐based catalysts with polarons to create orderly and asymmetric substructures as active sites for efficient electrocatalysis in PEMWE application.
Direct Access to α,β‐Unsaturated γ‐Lactams via Palladium‐Catalysed Carbonylation of Propargylic Ureas.
Authors: Schiroli Debora , Voronov Aleksandr , Pancrazzi Francesco , Iraci Nunzio , Vincenzo Giofrè Salvatore , Macchi Beatrice , Stefanizzi Valeria , Mancuso Raffaella , Gabriele Bartolo , Pio Mazzeo Paolo , Capaldo Luca , Della Ca' Nicola 
Published: November 2024

AbstractAdditive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment of the PdI2/KI catalytic system allowed complete regioselectivity (5‐endo‐dig), high functional group tolerance, broad substrate scope as well as operational simplicity (oxidant‐free, organic ligand‐free and base‐free protocol). The synthetic utility of these γ‐lactams is showcased through late‐stage functionalizations, such as Giese reactions and peptide couplings.
N‐Oxide‐Catalyzed Six‐Membered Ring Bromo‐Etherification of ϵ‐Alkenyl Alcohols
Authors: Hoshino Yuki , Kasahara Honoka , Marushima Ryusei , Moriyama Katsuhiko 
Published: November 2024

AbstractA six‐membered ring bromo‐etherification of ϵ‐alkenyl alcohols using an N‐oxide catalyst was developed to furnish 2‐bromomethyl‐6‐substituted tetrahydropyrans with cis‐selectivity and 3‐bromomethyl isochromans in high yields. DFT calculations indicate that the NMO catalyst enhances the electrophilicity of the bromine atom on NBS via two hydrogen‐bonding interactions after the formation of the NMO‐NBS complex.
Landscape of the Peripheral Immune Response Induced by Intraoperative Radiotherapy Combined with Surgery in Early Breast Cancer Patients
Authors: Dai Danian , Li Xuerui , Zhuang Hongkai , Ling Yun , Chen Lezi , Long Cheng , Zhang Jinhui , Wang Yunjie , Li Yuehua , Tang Hailin , Chen Bo 
Published: November 2024

AbstractA comprehensive analysis of the immune response triggered by intraoperative radiation therapy (IORT) remains incomplete. In this study, single‐cell RNA sequencing and single‐cell T cell receptor sequencing are conducted on peripheral blood mononuclear cells (PBMCs) from patient with early‐stage breast cancer before and after IORT. Following IORT combined with surgery (defined as IORT+Surgery), PBMC counts remained stable, with increased proportions of T cells, mononuclear phagocytes, and plasma cells, and a reduction in neutrophil proportions. The cytotoxic score of CD8Teff_GZMK cells increased significantly post‐IORT. Communication between CD8Teff_GZMK cells and other immune cells via MIF_CD74 and MIF_TNFRSF14 is decreased after IORT. cDCs showed an upregulation of the MCH II signaling pathway, while memory B cells exhibited enhanced activation of the B cell pathway. T cell clones expanded significantly after treatment. IORT+Surgery demonstrated the ability to partially suppress the anti‐tumor effects of neutrophils. Flow cytometry analysis and co‐culture experiments are utilized to delve deeper into the functional alterations in T cells. IORT+Surgery significantly enhanced T cell cytotoxic activity. Blockade of PD‐1 of post‐IORT PBMCs shows higher T‐cell activity than that of pre‐IORT PBMCs. This research highlights IORT's impact on immune cells, offering insights for targeting immune responses in breast cancer.
Alphabet Handwriting Recognition: From Wood‐Framed Hydrogel Arrays Design to Machine Learning Decoding
Authors: Yan Guihua , Hu Xichen , Miao Ziyue , Liu Yongde , Zeng Xianhai , Lin Lu , Ikkala Olli , Peng Bo 
Published: November 2024

AbstractHandwriting recognition is a highly integrated system, demanding hardware to collect handwriting signals and software to deal with input data. Nonetheless, the design of such a system from scratch with sustainable materials and an easily accessible computing network presents significant challenges. In pursuit of this goal, a flexible, and electrically conductive wood‐derived hydrogel array is developed as a handwriting input panel, enabling recognizing alphabet handwriting assisted by machine learning technique. For this, lignin extraction‐refill, polypyrrole coating, and polyacrylic acid filling, endowing flexibility, and electrical conduction to wood are sequentially implemented. Subsequently, these woods are manufactured into a 5 × 5 array, creating a matrix of signals upon handwriting. Efficient handwritten recognition is then achieved through appropriate manual feature extraction and algorithms with low complexity within a computing network, as demonstrated in this work, the strategic choice of expertise‐based feature engineering and simplified algorithms effectively boost the overall model performance on handwriting recognition. With potential adaptability, further applications in customized wearable devices and hands‐on healthcare appliances are envisioned.
Super‐Enhancer Reprograming Driven by SOX9 and TCF7L2 Represents Transcription‐Targeted Therapeutic Vulnerability for Treating Gallbladder Cancer
Authors: Yan Siyuan , Liu Zhaonan , Wang Teng , Sui Yi , Wu Xiangsong , Shen Jiayi , Pu Peng , Yang Yang , Wu Sizhong , Qiu Shimei , Wang Ziyi , Jiang Xiaoqing , Feng Feiling , Li Guoqiang , Liu FaTao , Zhao Chaoxian , Liu Ke , Feng Jiayi , Li Maolan , Man Kwan , Wang Chaochen , Tang Yujie , Liu Yingbin 
Published: November 2024

AbstractGallbladder cancer (GBC) is a highly aggressive malignancy lacking clinically available targeted therapeutic agents. Super‐enhancers (SEs) are crucial epigenetic cis‐regulatory elements whose extensive reprogramming drives aberrant transcription in cancers. To study SE in GBC, the genomic distribution of H3K27ac is profiled in multiple GBC tissue and cell line samples to establish the SE landscape and its associated core regulatory circuitry (CRC). The biliary lineage factor SOX9 and Wnt pathway effector TCF7L2, two master transcription factor (TF) candidates identified by CRC analysis, are verified to co‐occupy each other's SE region, forming a mutually autoregulatory loop to drive oncogenic SE reprogramming in a subset of GBC. The SOX9/TCF7L2 double‐high GBC cells are highly dependent on the two TFs and enriched of SE‐associated gene signatures related to stemness, ErbB and Wnt pathways. Patients with more such GBC cells exhibited significantly worse prognosis. Furthermore, SOX9/TCF7L2 double‐high GBC preclinical models are found to be susceptible to SE‐targeted CDK7 inhibition therapy in vitro and in vivo. Together, this study provides novel insights into the epigenetic mechanisms underlying the oncogenesis of a subset of GBCs with poorer prognosis and illustrates promising prognostic stratification and therapeutic strategies for treating those GBC patients in future clinical trials.
Bacteria‐Mediated Tumor‐Targeting Delivery of Multienzyme‐Mimicking Covalent Organic Frameworks Promoting Pyroptosis for Combinatorial Sono‐Catalytic Immunotherapy
Authors: Liu Yunyun , Xiang Lihua , Li Yitong , Zhang Shen , Zhang Ying , Shi Hui , Liu Hui , Du Dou , Zhou Bangguo , Ye Beibei , Li Shaoyue , Yin Haohao , Xu Huixiong , Zhang Yifeng 
Published: November 2024

AbstractPyroptosis, an inflammatory cell death, has attracted great attention for potentiating a strong immune response against tumor cells. However, developing powerful pyroptosis inducers and then activating specific pyroptosis still remains challenging. Herein, a PEG‐CuP‐COF@∆St nanosystem is rationally designed, consisting of PEG‐CuP‐COF nanozyme pyroptosis inducers and tumor‐targeting bacteria of the Salmonella Typhimurium strain VNP20009 (ΔSt), with an affinity for the tumor hypoxic microenvironment. The PEG‐CuP‐COF nanozymes possessed excellent sonodynamic performance and multienzyme‐mimicking activities to generate reactive oxygen species (ROS) and then induce potent pyroptosis. The superoxide dismutase‐ and peroxidase‐mimicking activities of PEG‐CuP‐COF catalytically produced hydrogen peroxide (H2O2) and hydroxyl radicals (•OH) which have important value in triggering acute inflammatory responses and pyroptosis. Moreover, PEG‐CuP‐COF showed outstanding glutathione peroxidase‐mimicking activities, impairing the antioxidant defense in tumor cells and enhancing sonodynamic efficiency by making them more vulnerable to ROS‐induced damage. During in vivo studies, PEG‐CuP‐COF@∆St nanosystem with its self‐driven property exhibited impressive tumor‐targeting capability and activated Caspase‐3/gasdermin E‐dependent pyroptosis to inhibit tumor growth. More importantly, it induced a powerful immune memory effect to prevent bone metastasis. In summary, this study introduces an innovative approach for combinatorial sono‐catalytic immunotherapy using bacteria‐mediated tumor‐targeting delivery of nanozymes as specific pyroptosis inducers.
Engineering a Mesoporous Silicon Nanoparticle Cage to Enhance Performance of a Phosphotriesterase Enzyme for Degradation of VX Nerve Agent
Authors: Lu Yi‐Sheng , Moreno Eduardo Reynoso , Huang Yubin , Fan Ruhan , Tucker Ashley T. , Wright Linnzi K. , Evans Ronald A. , Ahern Brooke M. , Owens Donald E. , Chappell Stephen A. , Christensen Dale J. , Dresios John , Sailor Michael J. 
Published: November 2024

AbstractThe organophosphate (OP)‐hydrolyzing enzyme phosphotriesterase (PTE, variant L7ep‐3a) immobilized within a partially oxidized mesoporous silicon nanoparticle cage is synthesized and the catalytic performance of the enzyme@nanoparticle construct for hydrolysis of a simulant, dimethyl p‐nitrophenyl phosphate (DMNP), and the live nerve agent VX is benchmarked against the free enzyme. In a neutral aqueous buffer, the optimized construct shows a ≈2‐fold increase in the rate of DMNP turnover relative to the free enzyme. Enzyme@nanoparticles with more hydrophobic surface chemistry in the interior of the pores show lower catalytic activity, suggesting the importance of hydration of the pore interior on performance. The enzyme@nanoparticle construct is readily separated from the neutralized agent; the nanoparticle is found to retain DMNP hydrolysis activity through seven decontamination/recovery cycles. The nanoparticle cage stabilizes the enzyme against thermal denaturing and enzymatic (trypsin) degradation conditions relative to free enzyme. When incorporated into a topical gel formulation, the PTE‐loaded nanoparticles show high activity toward the nerve agent VX in an ex vivo rabbit skin model. In vitro acetylcholinesterase (AChE) assays in human blood show that the enzyme@nanoparticle construct decontaminates VX, preserving the biological function of AChE when exposed to an otherwise incapacitating dose.
MnO2 Nanowires with Sub‐10 nm Thick Conjugated Microporous Polymers as Synergistic Triboelectric Materials
Authors: Jung Hanbyeol , Lee Dong‐Min , Park Jina , Kim Taeho , Kim Sang‐Woo , Son Seung Uk 
Published: November 2024

AbstractMnO2 nanowires coated with conjugated microporous polymers (CMP) are applied as triboelectric energy harvesting materials. The tribopositive performance of the CMP shells is enhanced with the assistance of MnO2 nanowires (MnO2 NW), likely due to cationic charge transfer from the tribopositive CMP layers to the surface Mn2+ and Mn3+ species of MnO2 NW. This is supported by model studies. The MnO2@CMP‐2 with sub‐10 nm thick CMP layers shows promising triboelectric output voltages up to 576 V and a maximum power density of 1.31 mW cm−2. Spring‐assisted triboelectric nanogenerators fabricated with MnO2@CMP‐2/PVP‐3 films are used as power supplies to operate electronic devices.
Investigations of Mechanisms Leading to Capacity Differences in Li/Na/K‐Ion Batteries with Conversion‐Type Transition‐Metal Sulfides Anodes
Authors: Zheng Kunxiong , Mu Yongbiao , Han Meisheng , Liu Jie , Zou Zhiyu , Hu Hengyuan , Chu Youqi , Yu Fenghua , Li Wenjia , Wei Lei , Zeng Lin , Zhao Tianshou 
Published: November 2024

AbstractConversion‐type transition‐metal sulfides (CT‐TMSs) have been extensively studied as the anode of Li/Na/K‐ion batteries due to their high theoretical capacity. An issue with the use of the material in the battery is that a large capacity difference is commonly observed. However, the underlying mechanism leading to the problem is still unknown. Here, the large capacity difference mechanisms of CT‐TMSs anodes in the Li/Na/K‐ion storage are elucidated, which arises from the difference in conversion degree and size of conversion products. Specifically, the increase in ionic radius will cause the increase in insertion‐reaction ion diffuse energy barrier and conversion‐reaction Gibbs free energies of phase transformation to decrease reaction kinetics, which causes a decrease in conversion degree and an increase in size of conversion products, thus leading to reduction in capacity. The increase in size and the decrease in the amount of conversion products inevitably reduce the amount of spin‐polarized electrons injection into Fe and corresponding ions storage amount into sulfides during the ion‐electron decoupling storage, thus reducing the capacity. The research clarifies the capacity difference mechanisms of CT‐TMSs anodes in Li/Na/K storage, providing valuable insights for designing Li/Na/K storage high‐capacity anodes.
Oxygen Defect Site Filling Strategy Induced Moderate Enrichment of Reactants for Efficient Electrocatalytic Biomass Upgrading
Authors: Cheng Baixue , Zhan Haoyu , Lu Yankun , Xing Danning , Lv Xingshuai , Frauenheim Thomas , Zhou Peng , Wang Shuangyin , Zou Yuqin 
Published: November 2024

AbstractThe electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) provides a feasible approach for the efficient utilization of biomass. Defect regulation is an effective strategy in the field of biomass upgrading to enhance the adsorption capacity of reactants and thus increase the activity. However, how to select appropriate strategies to regulate the over‐enrichment of reactants induced by excessive oxygen vacancy is still a huge challenge. In this work, the defect‐filling strategy to design and construct an element‐filled oxygen vacancy site layered double hydroxide (S─Ov─LDH) is adopted, which achieves a significant reduction in the electrolysis potential of biomass platform molecule HMF oxidation reaction and a significant increase in current density. Physical characterizations, electrochemical measurements, and theoretical calculations prove that the formation of metal─S bond in the second shell effectively regulates the electronic structure of the material, thus weakening the over‐strong adsorption of HMF and OH− induced by excessive oxygen vacancy, promoting the formation of high‐valence Co3+ during the reaction, and forming new adsorption sites. This work discusses the catalytic enhancement mechanism of defect filling in detail, fills the gap of defect filling in the field of biomass upgrading, and provides favorable guidance for the further development of defect regulation strategies.
Halogenated Polycyclic Aromatic Hydrocarbon for Hole Selective Layer/Perovskite Interface Modification and Passivation for Efficient Perovskite‐Organic Tandem Solar Cells with Record Fill Factor
Authors: Mahmud Md Arafat , Zheng Jianghui , Chang Jia‐Fu , Wang Guoliang , Liao Chwenhaw , Rahman Md Habibur , Tarique Walia Binte , Tang Shi , Bing Jueming , Bailey Christopher G. , Li Zhuofeng , Yang Limei , Novikova Nina , Leung Tik Lun , Chen Hongjun , Yi Jianpeng , Tao Runmin , Jankovec Marko , Bremner Stephen P. , Cairney Julie , Uddin Ashraf , Nguyen Hieu T. , Smith Trevor , Chueh Chu‐Chen , Ho‐Baillie Anita W. Y. 
Published: November 2024

AbstractPerovskite whentandemed with organic photovoltaics (OPV) for double‐junctions have efficiencypotentials over 40%. However, there is still room for improvement suchas better current matching, higher fill factor, as well as lower voltage and fill factor losses in the top perovskite cell. Here weaddress the issue associated with the top perovskite cell by utilising anovel halogenated polycyclic aromatic hydrocarbon compound, 1‐naphthylammoniumchloride (NA─Cl) playing dual roles of surface modification for the hole selectivelayer (HSL) and passivation of HSL/perovskiteinterface. Results of X‐ray photoelectron spectroscopy and density functionaltheory calculations reveal that NA─Cl retains self‐assembly property for the HSLwhile demonstrating high dipole moment and polarizability. This induces asurface dipole at the HSL/perovskite interface reducing the energetic barrierfor hole extraction by 210 meV thereby enhancing voltage output and fill factorof the device. Such scheme when implemented in a high bandgap (1.78 eV)perovskite solar cell, results in a respectable efficiency of 19.7% and thehighest fill factor of 85.4% amongst those of 1.78 eV perovskite cells reported.We have also achieved 23% cell efficient monolithic perovskite‐OPV tandem withan impressive fill factor of 84%, which is the highest for perovskite‐OPVtandem cells reported to‐date.
Photoclick and Release for Spatiotemporally Localized Theranostics of Single Cells via In Situ Generation of 1,3‐Diaryl‐1H‐benzo[f]indazole‐4,9‐dione
Authors: Li Bao‐Lin , Li Sitong , Zhang Cefei , Zhou Yuqiao , Zhao Xiaohu , Yu Zhipeng 
Published: November 2024

AbstractBioorthogonal click‐release chemistry is a cutting‐edge tool for exploring and manipulating biomolecule functions in native biological systems. However, it is challenging to achieve the precise regulation or therapy of individual cells via click‐release strategies driven by proximity and thermodynamics. Herein, we propose a novel photoclick‐release approach based on a photo‐induced cycloaddition between 4,4′‐bis(N‐arylsydnone) or C‐bithienyl‐diarylsydnone and 2‐arylamino‐naphthoquinone via irradiation with 405 or 485 nm light. It constructs 1,3‐diaryl‐1H‐benzo[f]indazole‐4,9‐dione (BIZON) as a pharmacophore while releases an arylamine for fluorescence turn‐on probing. Both photoclick reagents were tailored by connecting to the triphenyl phosphonium delivery motif for enrichment in the mitochondria of live cells. This enables an intracellular photoclick and release under the control of 405 or 485 nm light. We then discovered that the in situ photo‐generated BIZON is capable of photosensitizing upon 485 or 520 nm light to produce singlet oxygen inside the mitochondria under aerobic conditions. Therefore, we realized wash‐free fluorescence tracking and subsequent anti‐cancer efficacy at single‐cell resolution using global illumination, which provides a foundation for wavelength‐gated single‐cell theranostics.