bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineering Antibonding Orbital Occupancy for Enhanced Sodium‐Ion Intercalation Kinetics in Transition Metal Oxides
Authors: Wang Jinrui , Liu Yuanming , Hou Zishan , Wang Shiyu , Yao Shuyun , Gao Xueying , Zhang Huiying , Tang Zheng , Nie Kaiqi , Xie Jiangzhou , Yang Zhiyu , Yan Yi‐Ming 
Published: February 2024

AbstractIn the quest to elevate the sodium‐ion intercalation kinetics of transition metal oxide electrodes, the intrinsic low conductivity of these materials often acts as a bottleneck, restricting Na+ storage. Herein, the mechanism behind sodium‐ion diffusion kinetics in MnO2 is explored, specifically focusing on the manipulation of π* antibonding orbital occupancy. This is accomplished through strategic doping with strongly electron‐withdrawing Rh3+ (t2g6eg0), enhancing the hybridization of Mn 3d‐O 2p orbitals and significantly increasing the electrical conductivity of MnO2. Density functional theory (DFT) calculations and X‐ray absorption spectroscopy (XAS) results demonstrate that the smaller orbital energy difference between Rh3+ eg and Mn4+ t2g, compared to that between Rh3+ eg and Mn4+ eg, fosters direct electron transfer from the Mn4+ t2g to the vacant Rh3+ eg. This electron movement induces an upshift in the Mn‐t2g orbital energy levels while concurrently diminishing the occupancy of π* antibonding orbitals formed via Mn t2g‐O 2p hybridization. The resultant Rh‐MnO2 electrode exhibits an impressive specific capacity of 335 F g−1 at 1 A g−1 and a substantial rate capacity of 224.8 F g−1 at 20 A g−1. This investigation elucidates the intricate mechanism underlying the sluggish kinetics of sodium ion intercalation within transition metal oxide frameworks.
Natural Sunlight‐Driven CO2 Hydrogenation into Light Olefins at Ambient Pressure over Bifunctional Cu‐Promoted CoFe Alloy Catalyst
Authors: Ning Shangbo , Wang Junwei , Wu Xiuting , Li Ling , Zhang Senlin , Chen Shaohua , Ren Xiaohui , Gao Linjie , Hao Yuchen , Lv Cuncai , Li Yaguang , Ye Jinhua 
Published: February 2024

AbstractThe natural sunlight‐driven conversion of CO2 into valuable C2+ products is urgently being pursued at ambient pressure, yet it poses a substantial challenge. Herein, a bifunctional Cu‐promoted CoFe alloy catalyst is designed for the natural light‐driven CO2 hydrogenation into light olefins. Under a weak solar‐irradiation intensity of 0.45 kW m−2 (0.45 sun), the optimal catalyst exhibits excellent activity and selectivity, with an impressive 73.7% selectivity for C2+ hydrocarbons and an outstanding 56.5% selectivity for C2‐4 olefins, which is the best catalyst for C2+ hydrocarbons photosynthesis from natural sunlight to date. The bifunctional design of the catalyst combines the advantages of both metallic Cu and CoFe alloy components, providing a synergistic effect that enhances the CO2 hydrogenation performance. The Cu promoter plays a crucial role in enhancing the adsorption of CO2 and hydrogen spillover, while the CoFe alloy provides a stable coupling site of the C1 intermediate for promoting the C2‐4 olefins. This study provides new insights into the design of bifunctional catalysts for CO2 hydrogenation and opens up new possibilities for sustainable production of light olefins from renewable resources.
Controlled Refolding of Denatured IL‐12 Using In Situ Antigen‐Capturing Nanochaperone Remarkably Reduces the Systemic Toxicity and Enhances Cancer Immunotherapy
Authors: Zhang Yongxin , Ma Feihe , Chen Jiajing , Chen Yujie , Xu Linlin , Li Ang , Liu Yang , Ma Rujiang , Shi Linqi 
Published: February 2024

AbstractCytokines are powerful in cancer immunotherapy, however, their therapeutic potential is limited by the severe systemic toxicity. Here a potent strategy to reduce the toxicity of systemic cytokine therapy by delivering its denatured form using a finely designed nanochaperone, is described. It is demonstrated that even if the denatured protein cargos are occasionally released under normal physiological conditions they are still misfolded, while can effectively refold into native states and release to function in tumor microenvironment. Consequently, the systemic toxicity of cytokines is nearly completely overcome. Moreover, an immunogenic cell death (ICD)‐inducing chemotherapeutic is further loaded and delivered to tumor using this nanochaperone to trigger the release of tumor‐associated antigens (TAAs) that are subsequently captured in situ by nanochaperone and then reflows into lymph nodes (LNs) to promote antigen cross‐presentation. This optimized personalized nanochaperone‐vaccine demonstrates unprecedented suppressive effects against large, advanced tumors, and in combination with immune checkpoint blockade (ICB) therapy results in a significant abscopal effect and inhibition of postoperative tumor recurrence and metastasis. Hence, this approach provides a simple and universal delivery strategy to reduce the systemic toxicities of cytokines, as well as provides a robust personalized cancer vaccination platform, which may find wide applications in cancer immunotherapy.
Ultra‐Sensitive and Stable Multiplexed Biosensors Array in Fully Printed and Integrated Platforms for Reliable Perspiration Analysis
Authors: Ma Suman , Wan Zhu'an , Wang Chen , Song Zhilong , Ding Yucheng , Zhang Daquan , Chan Chak Lam Jonathan , Shu Lei , Huang Liting , Yang Zhensen , Wang Fei , Bai Jiaming , Fan Zhiyong , Lin Yuanjing 
Published: February 2024

AbstractElectrochemical biosensors have emerged as one of the promising tools for tracking human body physiological dynamics via non‐invasive perspiration analysis. However, it remains a key challenge to integrate multiplexed sensors in a highly controllable and reproducible manner to achieve long‐term reliable biosensing, especially on flexible platforms. Herein, a fully inkjet printed and integrated multiplexed biosensing patch with remarkably high stability and sensitivity is reported for the first time. These desirable characteristics are enabled by the unique interpenetrating interface design and precise control over active materials mass loading, owing to the optimized ink formulations and droplet‐assisted printing processes. The sensors deliver sensitivities of 313.28 µA mm−1 cm−2 for glucose and 0.87 µA mm−1 cm−2 for alcohol sensing with minimal drift over 30 h, which are among the best in the literature. The integrated patch can be used for reliable and wireless diet monitoring or medical intervention via epidermal analysis and would inspire the advances of wearable devices for intelligent healthcare applications.
Sustained and Localized Drug Depot Release Using Radiation‐Activated Scintillating Nanoparticles
Authors: Kang Mikyung , Quintana Jeremy , Hu Huiyu , Teixeira Verônica C. , Olberg Sven , Banla Leou Ismael , Rodriguez Victoria , Hwang William L. , Schuemann Jan , Parangi Sareh , Weissleder Ralph , Miller Miles A. 
Published: February 2024

AbstractClinical treatment of cancer commonly incorporates X‐ray radiation therapy (XRT), and developing spatially precise radiation‐activatable drug delivery strategies may improve XRT efficacy while limiting off‐target toxicities associated with systemically administered drugs. Nevertheless, achieving this has been challenging thus far because strategies typically rely on radical species with short lifespans, and the inherent nature of hypoxic and acidic tumor microenvironments may encourage spatially heterogeneous effects. It is hypothesized that the challenge could be bypassed by using scintillating nanoparticles that emit light upon X‐ray absorption, locally forming therapeutic drug depots in tumor tissues. Thus a nanoparticle platform (Scintillating nanoparticle Drug Depot; SciDD) that enables the local release of cytotoxic payloads only after activation by XRT is developed, thereby limiting off‐target toxicity. As a proof‐of‐principle, SciDD is used to deliver a microtubule‐destabilizing payload MMAE (monomethyl auristatin E). With as little as a 2 Gy local irradiation to tumors, MMAE payloads are released effectively to kill tumor cells. XRT‐mediated drug release is demonstrated in multiple mouse cancer models and showed efficacy over XRT alone (p < 0.0001). This work shows that SciDD can act as a local drug depot with spatiotemporally controlled release of cancer therapeutics.
Sub‐Micron Thickness Self‐Limiting Electrospray Deposition via Voltage Bias of Spray Target
Authors: Rouf Ayman , Park Sarah H. , Singer Jonathan P. 
Published: February 2024

AbstractElectrospray deposition (ESD) is a technique with emerging relevance for applications requiring micro‐/nano‐scaled coatings. Self‐limiting electrospray deposition (SLED) is a regime of ESD where upon satisfying the criteria for self‐limiting behavior, the charge buildup of the material will eventually begin to repel itself until an asymptotic thickness is achieved, based primarily on the properties of the spray solution and deposited material. This work focuses on controlling the coating thickness further to achieve sub‐micron thicknesses. By applying a voltage bias of the same polarity of the spray onto the target substrate while providing a secondary grounded surface, the thickness of a payload can be manipulated for thinner and more precise thicknesses. The magnitude of the voltage bias is varied to show the effect of voltage bias on thickness, and 2‐D and 3‐D structures are used to demonstrate the generality of this technique for complex substrates. The results show how SLED can be included as a potential alternative for conformal coatings deposited at ambient conditions at the sub‐micron scale.
A Microfluidic Perfusion Culture Setup to Investigate Cell Migration in 3D Constrictions
Authors: Geiger Matthias , Marsico Prianca , Pensold Daniel , Wessling Matthias , Zimmer‐Bensch Geraldine , Linkhorst John 
Published: February 2024

AbstractCell migration is a fundamental process underlying the morphological maturation of organs, but also in disease‐related conditions such as cancer. Cells are able to migrate through crowded space and a tight extracellular matrix (ECM). Passing through a constriction, a cell deforms strongly, including its nucleus. Such nuclear deformation can lead to changes in the 3D‐genomic architecture, and putatively, DNA methylation. However, the specific effects of deformation on cells are not well understood. It is highly desired to establish an ex vivo methodology to induce well‐defined cell deformation in complex geometrical constrictions. This study introduces a microfluidic system for the study of migrating cells in precisely controlled geometrical confinement. A procedure for coating, seeding of cerebellar granule cells, and perfusion culture is presented. By leveraging direct laser writing, channels with smooth, anisotropically curved surfaces on the cell‐scale can be fabricated. The system consists of constriction channels with a radius of 2 or 4 µm for the cells to pass through. This corresponds to a compression of the nucleus to 3.5% and 14.2% of its undeformed cross‐sectional area, respectively. The system can be used to investigate the influence of confinement geometry on the migration behavior and transcriptome of various cell types.
Nanoparticle‐Mediated Tumor Microenvironment Remodeling Favors the Communication with the Immune Cells for Tumor Killing
Authors: Lucena‐Sánchez Elena , Hicke Francisco J. , Clara‐Trujillo Sandra , García‐Fernández Alba , Martínez‐Máñez Ramón 
Published: February 2024

AbstractMelanoma is one of the most common types of skin cancer with a bad prognosis and limited treatment options in advanced stages. Immunotherapy has changed the landscape of oncology. Cancer cells can activate various mechanisms to suppress immune responses, such as the immunological checkpoint programmed cell death‐1 (PD‐1)/programmed cell death‐ligand 1 (PD‐L1), whose blockage reactivates immune killing of melanoma cells. Moreover, exposure to inhibitory cytokines such as transforming growth factor‐beta (TGF‐β) induces T regulatory cell differentiation, which promotes cancer immunosuppression. These advances provided exciting outcomes in the clinical treatment of melanoma, however, there are still limitations, and a combination of several treatments is usually needed. Based on the above, inhibition of the TGF‐β production and the PD‐1/PD‐L1 checkpoint may be a feasible strategy to increase T cell infiltration and cytotoxicity and thus overcome tumor immune escape. Here, mesoporous silica nanoparticles loaded with a PD‐L1 inhibitor (JQ1, a thienotriazolodiazepine and a potent bromodomain family inhibitor) and capped with polyethyleneimine and a small interfering RNA targeting TGF‐β are reported. An efficient PD‐L1 downregulation and TGF‐β silencing are achieved using the nanoparticles, along with the promotion of cancer death. This system demonstrates to be a specific and innovative therapeutic approach for the treatment of melanoma.
Evaluation of dichlobenil for hair fescue (Festuca filiformis Pourr.) management in wild blueberry (Vaccinium angustifolium Ait.)
Authors: MacEachern Craig B. , Esau Travis J. , White Scott N. , Zaman Qamar U. , Farooque Aitazaz A. 
Published: February 2024

AbstractHair fescue is an economically destructive, tuft‐forming weed common in wild blueberry fields. The current management of hair fescue is almost completely reliant on pronamide (3,5‐dichloro‐N‐[2‐methylbut‐3‐yn‐2‐yl]benzamide) herbicide with few other products demonstrating effectiveness. Dichlobenil (2,6‐dichlorobenzonitrile) is a group 29 herbicide registered for use in wild blueberry; however, it has seen limited use because of its high product cost of over CAD 1800 ha−1 and limited research on the effect of varying application rates. Treatments (dichlobenil at 4400, 5700, and 7000 g a.i. ha−1, pronamide at 2240 g a.i. ha−1, and a nontreated control) were applied during the 2020 autumn prior to wild blueberry stem emergence in the nonbearing year (2021). Each treatment was replicated five times per field across three fields in central Nova Scotia. Dichlobenil at 4400, 5700, and 7000 g a.i. ha−1 reduced 2021 (nonbearing year) living tuft density by 59%, 71%, and 83%, respectively, and provided residual control in 2022 (bearing year) with densities reduced by 59%, 69%, and 78%, respectively. Comparatively, pronamide reduced 2021 and 2022 living tuft density by 95% and 91%. Reductions in living tuft density resulted in yield increases of 62%, 57%, and 94% in plots treated with dichlobenil at 4400, 5700, and 7000 g a.i. ha−1, respectively, and 73% for plots treated with pronamide. Results demonstrate that dichlobenil is an effective herbicide for managing hair fescue in wild blueberry. The potential for the selection of herbicide‐resistant biotypes to industry standard pronamide could be prolonged with integrated dichlobenil applications.
Biallelic OTUD6B variants associated with a Kabuki syndrome‐like disorder in three siblings: A clinical report and literature review
Authors: Gangaram Balram , Lee Virgina , Slavotinek Anne 
Published: February 2024

AbstractBiallelic variants in the OTUD6B gene have been reported in the literature in association with an intellectual developmental disorder featuring dysmorphic facies, seizures, and distal limb abnormalities. Physical differences described for affected individuals suggest that the disorder may be clinically recognizable, but previous publications have reported an initial clinical suspicion for Kabuki syndrome (KS) in some affected individuals. Here, we report on three siblings with biallelic variants in OTUD6B co‐segregating with neurodevelopmental delay, shared physical differences, and other clinical findings similar to those of previously reported individuals. However, clinical manifestations such as long palpebral fissures, prominent and cupped ears, developmental delay, growth deficiency, persistent fetal fingertip pads, vertebral anomaly, and seizures in the proband were initially suggestive of KS. In addition, previously unreported clinical manifestations such as delayed eruption of primary dentition, soft doughy skin with reduced sweating, and mirror movements present in our patients suggest an expansion of the phenotype, and we perform a literature review to update on current information related to OTUD6B and human gene‐disease association.
Lattice Strained Induced Spin Regulation in Co−N/S Coordination‐Framework Enhanced Oxygen Reduction Reaction
Authors: Lin Liu , Ni Youxuan , Shang Long , Wang Linyue , Yan Zhenhua , Zhao Qing , Chen Jun 
Published: February 2024

AbstractOxygen reduction reaction (ORR) is the bottleneck of metal‐air batteries and fuel cells. Strain regulation can change the geometry and adjust the surface charge distribution of catalysts, which is a powerful strategy to optimize the ORR activity. The introduction of controlled strain to the material is still difficult to achieve. Herein, we present a temperature‐pressure‐induced strategy to achieve the controlled lattice strain for metal coordination polymers. Through the systematic study of the strain effect on ORR performance, the relationship between geometric and electronic effects is further understood and confirmed. The strained Co‐DABDT (DABDT=2,5‐diaminobenzene‐1,4‐dithiol) with 2 % lattice compression exhibits a superior half‐wave potential of 0.81 V. Theoretical analysis reveals that the lattice strain changes spin‐charge densities around S atoms for Co‐DABDT, and then regulates the hydrogen bond interaction with intermediates to promote the ORR catalytic process. This work helps to understand the catalytic mechanism from the atomic level.
Independent Multiple‐Atom‐Site Functionality in Composition Adjustable Immiscible Ru‐Rh‐Pd‐Pt Solid‐Solution High‐Entropy Alloys for NOx Reduction Outperforming Rh
Authors: Tan Zhe , Huang Bo 
Published: February 2024

AbstractThe high‐entropy‐alloy (HEA) nanoparticles with four, five or more metals significantly can yield the developments of functional materials with excellent performances in various reactions. However, the underlying reaction mechanisms of heterogeneous catalysis for HEA have been rarely investigated, due to their diverse elements and complex compositions. In this study, we successfully synthesized the homogeneously dispersed Ru−Rh−Pd−Pt HEA with adjustable compositions, as the multiple‐atom‐site catalysts (MASC). In the NOx reduction performance tests, Ru0.4 (Rh0.33Pd0.33Pt0.33)0.6 MASC showed the highest activity, which was significantly improved compared to that of the best monometal Rh, with the light‐off temperature decreasing by ca. 50 °C. The Fourier transform infrared measurements revealed that the outstanding activity of Ru−Rh−Pd−Pt MASC was attributable to the well‐coupled elementary steps of the CO adsorption, NO adsorption, NO dissociation and O spillover on the Ru, Rh, Rh−Pd and Pt sites, respectively, which explained the first clear reaction mechanism in heterogeneous catalysis for HEA.
Glutathione Induced In situ Synthesis of Cu Single‐Atom Nanozymes with Anaerobic Glycolysis Metabolism Interference for Boosting Cuproptosis
Authors: Zhang Wenying , Wang Meifang , Liu Bin , Chen Hao , Tan Jia , Meng Qi , Li Jing , Ding Binbin , Ma Ping'an , Lin Jun 
Published: February 2024

AbstractSingle‐atom nanozyme (SAzyme) has sparked increasing interest for catalytic antitumor treatment due to their more tunable and diverse active sites than natural metalloenzymes in complex physiological conditions. However, it is usually a hard task to precisely conduct catalysis at tumor sites after intravenous injection of those SAzyme with high reactivity. Moreover, the explorations of SAzymes in the anticancer application are still in its infancy and need to be developed. Herein, an in situ synthesis strategy for Cu SAzyme was constructed to convert adsorbed copper ions into isolated atoms anchored by oxygen atoms (Cu−O2/Cu−O4) via GSH‐responsive deformability of supports. Our results suggest that the in situ activation process could further facilitate the dissociation of copper ions and the consumption of glutathione, thereby leading to copper deposition in cytoplasm and triggering cuproptosis. Moreover, the in situ synthesis of Cu SAzyme with peroxidase‐like activity enabled the intracellular reactive oxygen species production, resulting in specifically disturbance of copper metabolism pathway. Meanwhile, the in situ exposed glucose transporter (GLUT) inhibitor phloretin (Ph) can block the glycose uptake to boost cuproptosis efficacy. Overall, this in situ activation strategy effectively diminished the off‐target effects of SACs‐induced catalytic therapies and introduced a promising treatment paradigm for advancing cuproptosis‐associated therapies.
Tailoring the Electronic Metal‐Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation
Authors: Yang Hongling , Li Ganggang , Liu Qinggang , Cheng Haixia , Wang Xiaoxu , Cheng Jie , Jiang Guoxia , Zhang Fenglian , Zhang Zhongshen , Hao Zhengping 
Published: February 2024

AbstractMetal‐modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO2 support through strong electronic metal‐support interactions (EMSIs), overcoming the activity‐selectivity trade‐off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C2H4) and oxygen (O2) and facilitating EO desorption, resulting in high C2H4 conversion. Meanwhile, the increased number of positively charge Ag+ lowers the energy barrier for C2H4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.
Potential of Pinhão husk (Araucaria angustifolia) as a structural reinforcement agent in the properties of edible films of Pinhão flour and gelatin
Authors: De Santana Neto Deocleciano Cassiano , Paiva Thainnane Silva , Dos Santos Rogério Willian Silva , Helm Cristiane Vieira , Da Silva Fábio Anderson Pereira , De Matos Jorge Luiz Mário , Jorge Regina Maria Matos 
Published: February 2024

AbstractIn this study, the use of Pinhão husk as a source of reinforcement material for development of edible films, where the Pinhão seed flour and bovine gelatin were used as matrices for the films. Mechanical properties, water vapor permeability, solubility and opacity, microstructure, and thermal degradation characterized the films produced. The films presented homogeneous and cohesive structures. Pinhão husk content positively affected film properties by increasing tensile strength (TS) and decreasing water vapor permeability (WVP), with Pinhão flour film formulations (5.0% Pinhão flour, 1.2% glycerol, and 0.4% Pinhão husk) and gelatin (5.0% gelatin, 2.0% glycerol, and 0.4% Pinhão husk) those that presented the best results (5.06 MPa for TS and 0.14 g.mm/kPa.h.m2 for WVP) and (3.88 MPa for TS and 0.28 g.mm/kPa.h.m2 for WVP), respectively The thermal degradation study revealed that the films are stable at temperatures below 150°C, losing only free water and volatile compounds of low molecular weight. Pinhão husk can reinforce films, making them suitable as biodegradable and edible packaging materials for eco‐friendly food products. This contributes to the circular economy, preserves biodiversity, and reduces plastic waste, offering promising sustainable packaging solutions.