bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photo‐Facilitated Nitric Oxide‐Triggered Turn‐on Photodynamic Therapy for Precise Antitumor Application
Authors: Qin Yiliang , Gao Hanyi , Yin Yuting , Li Jiayi , He Xia , Gao Meng , Sun Liying , Yuan Yi , Tian Ying , Zhou Yizhao , Zeng Zebing , Zhang Xiaodong , Hu Rong 
Published: January 2025

AbstractPhotodynamic therapy (PDT) is a powerful strategy for tumor therapy with noninvasiveness and desirable efficacy. However, the phototoxicity of photosensitizer after the post‐PDT is the major obstacle limiting the clinic applications. Herein, a nitric oxide (NO)‐activatable photosensitizer is reported with turn‐on PDT behavior and endoplasmic reticulum (ER) targeting ability for precise tumor therapy. Four o‐thiophenediamine derivatives with reaction‐tunable donor/acceptor push‐pull electronic effect are established, and the systematic structure and property relationship observation reveals the following features: 1) the reactivity against NO can be improved by enhancing the electron density and further facilitated upon photo‐irradiation. 2) the reactivity with NO enables the improved intramolecular charge transfer process with the evoking of photosensitizing effect. 3) only o‐thiophenediamine derivative with ER enrichment behavior exhibited cancer cell ablation effect compared to photosensitizers localized in lysosome and lipid droplet. Thus, the efficient inhibition of cancer cells both in vitro and in vivo is realized based on the photo‐controlled PDT strategy. This work provides more insights into developing promising activatable photosensitizers for advanced therapy based on tumor microenvironment trigger.
Metal‐Protein Hybrid Materials: Unlocking New Frontiers in Biomedical Applications
Authors: Pan Yong , Zhao Han , Huang Wenyong , Liu Siyang , Qi Yanxin , Huang Yubin 
Published: January 2025

AbstractMetal‐protein hybrid materials represent a novel class of functional materials that exhibit exceptional physicochemical properties and tunable structures, rendering them remarkable applications in diverse fields, including materials engineering, biocatalysis, biosensing, and biomedicine. The design and development of multifunctional and biocompatible metal‐protein hybrid materials have been the subject of extensive research and a key aspiration for practical applications in clinical settings. This review provides a comprehensive analysis of the design strategies, intrinsic properties, and biomedical applications of these hybrid materials, with a specific emphasis on their potential in cancer therapy, drug and vaccine delivery, antibacterial treatments, and tissue regeneration. Through rational design, stable metal‐protein hybrid materials can be synthesized using straightforward methods, enabling them with therapeutic, delivery, immunomodulatory, and other desired functionalities. Finally, the review outlines the existing limitations and challenges associated with metal‐protein hybrid materials and evaluates their potential for clinical translation, providing insights into their practical implementation within biomedical applications.
Untangling the Role of Capping Agents in Manipulating Electrochemical Behaviors Toward Practical Aqueous Zinc‐Ion Batteries
Authors: Chen Ruwei , Zhong Yunpeng , Jiang Peie , Tang Hao , Guo Fei , Dai Yuhang , Chen Jie , Wang Jingyi , Liu Jiyang , Wei Song , Zhang Wei , Zong Wei , Zhao Fangjia , Zhang Jichao , Guo Zhengxiao , Wang Xiaohui , He Guanjie 
Published: January 2025

AbstractLong‐standing challenges including notorious side reactions at the Zn anode, low Zn anode utilization, and rapid cathode degradation at low current densities hinder the advancement of aqueous zinc‐ion batteries (AZIBs). Inspired by the critical role of capping agents in nanomaterials synthesis and bulk crystal growth, a series of capping agents are employed to demonstrate their applicability in AZIBs. Here, it is shown that the preferential adsorption of capping agents on different Zn crystal planes, coordination between capping agents and Zn2+ ions, and interactions with metal oxide cathodes enable preferred Zn (002) deposition, water‐deficient Zn2+ ion solvation structure, and a dynamic cathode‐electrolyte interface. Benefiting from the multi‐functional role of capping agents, dendrite‐free Zn plating and stripping with an improved Coulombic efficiency of 99.2% and enhanced long‐term cycling stability are realized. Remarkable capacity retention of 91% is achieved for cathodes after more than 500 cycles under a low current density of 200 mA g−1, marking one of the best cycling stabilities to date. This work provides a proof‐of‐concept of capping agents in manipulating electrochemical behaviors, which should inspire and pave a new avenue of research to address the challenges in practical energy storage beyond AZIBs.
Atmospheric Water Sorption Kinetics in Powder and Monolithic Metal–Organic Frameworks
Authors: Li Jiawang , Wang Guang , Fan Hongzhao , Li Zhigang , Tso Chi Yan , Zhou Yanguang 
Published: January 2025

AbstractMetal–organic frameworks (MOFs) have been widely applied for adsorption applications owing to their high surface area and porosity. In this paper, the atmospheric water adsorption kinetics in a prototypical MOF with two forms, that is, powder and monolithic MOF‐801, are systematically investigated. It is shown that the total pore volume (average pore diameter) of the monolithic MOF‐801 is 0.831 cm3 g−1 (5.20 nm) which is much larger than that of powder MOF‐801, that is, 0.488 cm3 g−1 (1.95 nm). Monolithic MOF‐801 absorbs more water than powder MOF‐801 at a relative humidity (RH) above 90%. However, between the RH ranges from 10% to 90%, its water uptake is significantly lower than that of the powder form. Molecular dynamics simulations demonstrate that the unexpected water uptake capacity of monolithic MOF‐801 at RH of 10%∼90% is caused by the water film formed by the capillary condensation in these mesopores of monolithic MOF‐801. The capillary force of the formed film can be overcome by water vapor pressure when RH is over 90%. These findings reveal the underlying mechanisms for water adsorption kinetics in both powder and monolithic MOFs, which can motivate and benefit the new passive cooling or water harvesting system design based on MOFs.
Controlling Frost Propagation on Polymeric Surfaces Using SI‐ATRP Chemical Micropatterning
Authors: Tavaststjerna Miisa J. , Picken Stephen J. , Garcia Santiago J. 
Published: January 2025

AbstractMicropatterned surfaces with both hydrophilic and hydrophobic regions are relevant for a wide range of applications from fuel cells to water harvesting systems. The preferential nucleation of water on hydrophilic regions can also be used to control frost nucleation on chemically patterned surfaces. So far, this concept has been tested on brittle silicon surfaces with only a few different sizes and shapes of hydrophilic regions. In this work, the concept of controlled icing is investigated on five polymeric surfaces with different surface energies modified by micropatterning them with three types of hydrophilic polymer brushes. Frost formation and propagation on the resulting patterned surfaces with regions of varying wettability is monitored and quantified using high‐resolution thermal imaging. The study proves that control over frost nucleation and propagation using regions of varying wettability can be achieved on commodity polymers. In addition to influencing the time and location of ice nucleation, the local patterning affects the freezing propagation mode and rate due to its impact on the continuity and thickness of molecular water layers (MWL). These results show that local control over the state of MWLs is key to controlling both ice nucleation and propagation of freezing events on surfaces.
Temperature‐Dependent Properties of Atomic Layer Deposition‐Grown TiO2 Thin Films
Authors: Chowdhary Nimarta Kaur , Gougousi Theodosia 
Published: January 2025

AbstractThis study investigates the presence of titanium oxynitride bonds in titanium dioxide (TiO2) thin films grown by atomic layer deposition (ALD) using tetrakis dimethyl amino titanium (TDMAT) and water at temperatures between 150 and 350 °C and its effect on the films’ optical and electrical properties. Compositional analysis using X‐ray photoelectron spectroscopy (XPS) reveals increased incorporation of oxynitride bonds as the process temperature increases. Furthermore, depth profile data demonstrates an increase in the abundance of this type of bonding from the surface to the bulk of the films. Ultraviolet‐visible spectroscopy (UV‐vis) measurements correlate increased visible light absorption for the films with elevated oxynitride incorporation. The optical constants (n, k) of the films show a pronounced dependence on the process temperature that is mirrored in the film conductivity. The detection of oxynitride bonding suggests a secondary reaction pathway in this well‐established ALD process chemistry, that may impact film properties. These findings indicate that the choice of process chemistry and conditions can be used to optimize film properties for optoelectronic applications.
Heterostructured Lanthanide Perovskite Nanoparticles with High Quantum Yield and Water Stability for Optical Information Storage
Authors: Li Jiwei , Sun Renrui , Chen Jiabo , Su Qichen , Xie Yao , Sun Guotao , Zhang Hui , Sun Lining 
Published: January 2025

AbstractIn this study, heterostructured nanoparticles based on lanthanide double perovskite halide are innovatively proposed, which dramatically improved quantum yield and color purity, but the problem of water stability of perovskite materials has also been solved. The nanoparticles without surface ligands have excellent stability and optical properties when dispersed in water, and have higher color purity than those dispersed in organic solvents. Besides, the application potential is demonstrated and the practical performance is verified by preparing luminescent ink. This study provides a new strategy for the performance enhancement and application prospect of lanthanide double perovskite.
Multifunctionalization of N‐Heterocyclic Carbene Boranes by a Single Metal‐free Photocatalyst
Authors: Li Feng‐Xing , Liu Yu , Zhang Ke , Wang Cheng , Yu Ji‐Xin , He Xiao‐Jun , Liang Ge , Hou Hong‐Yu , Tung Chen‐Ho , Wu Li‐Zhu 
Published: January 2025

AbstractSelective access to densely functionalized boranes, with identical or distinct functional groups at the boron center, has great potentials in materials science, organic synthesis and drug discovery. However, assembling multifunctional boranes was heavily dependent on hydrogen‐atom‐transfer (HAT) at high temperatures, hazardous radical initiators, metal photocatalysts and HAT reagents, respectively. Simultaneously, competitive side reactions such as polymerizations and regioisomers formation remain highly challenging. Herein, a programmable multifunctionalization of N‐heterocyclic carbene (NHC) boranes is developed for the first time powered by a single, metal‐free photocatalyst, in which boryl radicals from sequential substituted boranes are generated instead of polymerizations. This robust and versatile catalytic system leads to an extremely broad variety of boranes incorporated with diverse alkyl or alkenyl groups in high chemo‐ and regioselectivities.
Synthesis of 2‐Aminoquinazolines through I2‐Catalyzed Cyclization of 2‐Aminoaryl Ketone Oximes and Isocyanides
Authors: Lin Huishu , Huang Rongxiuyuan , Wang Xu , Fu Jinping , Liu Yuyuan , Yi Yi , Pan Yingming 
Published: January 2025

AbstractAn I2/cumene hydroperoxide (CHP)‐mediated tandem cyclization of 2‐aminoaryl ketone oximes with isocyanides has been developed. Various 2‐aminoquinazolines were obtained in 49–96% yields under transition‐metal‐free conditions, and the resulting 4‐phenylquinazolin‐2‐amines show typical fluorescent emission properties. The key to the success of this strategy involves the formation of iminyl radical via the N−O bond cleavage of hydroxy oxime.
Unraveling Spatial Heterogeneity in Mass Spectrometry Imaging Data with GraphMSI
Authors: Guo Lei , Xie Peisi , Shen Xionghui , Lam Thomas Ka Yam , Deng Lingli , Xie Chengyi , Xu Xiangnan , Wong Chris Kong Chu , Xu Jingjing , Fang Jiacheng , Wang Xiaoxiao , Xiong Zhuang , Luo Shangyi , Wang Jianing , Dong Jiyang , Cai Zongwei 
Published: January 2025

AbstractMass spectrometry imaging (MSI) provides valuable insights into metabolic heterogeneity by capturing in situ molecular profiles within organisms. One challenge of MSI heterogeneity analysis is performing an objective segmentation to differentiate the biological tissue into distinct regions with unique characteristics. However, current methods struggle due to the insufficient incorporation of biological context and high computational demand. To address these challenges, a novel deep learning‐based approach is proposed, GraphMSI, which integrates metabolic profiles with spatial information to enhance MSI data analysis. Our comparative results demonstrate GraphMSI outperforms commonly used segmentation methods in both visual inspection and quantitative evaluation. Moreover, GraphMSI can incorporate partial or coarse biological contexts to improve segmentation results and enable more effective three‐dimensional MSI segmentation with reduced computational requirements. These are facilitated by two optional enhanced modes: scribble‐interactive and knowledge‐transfer. Numerous results demonstrate the robustness of these two modes, ensuring that GraphMSI consistently retains its capability to identify biologically relevant sub‐regions in complex practical applications. It is anticipated that GraphMSI will become a powerful tool for spatial heterogeneity analysis in MSI data.
Freestanding Membranes of Titania Nanorods, Photocatalytically Reduced Graphene Oxide, and Silk Fibroin: Tunable Properties and Electrostatic Actuation
Authors: Dobschall Finn , Hartmann Hauke , Bittinger Sophia Caroline , Schulz Norbert , Schlicke Hendrik , Trieu Hoc Khiem , Vossmeyer Tobias 
Published: January 2025

AbstractIn this study, the mechanical properties of freestanding membranes made of graphene oxide (GO), titania nanorods (TNRs), and silk fibroin (SF) are investigated and their application is demonstrated as electrostatically driven actuators. Using a stamping process, the membranes are transferred onto substrates with circular apertures or square cavities measuring ∼80 to 245 µm in diameter or edge length, respectively. Afterwards, the membranes are exposed to deep‐UV (DUV) radiation in order to photocatalytically convert GO to reduced graphene oxide (rGO). Microbulge tests combined with atomic force microscopy (AFM) measurements reveal enhanced mechanical stability after the DUV treatment, as indicated by an increase of Young's modulus from ∼22 to ∼35 GPa. The toughness of the DUV‐treated membranes is up to ∼1.25 MJ m−3, while their ultimate biaxial tensile stress and strain are in the range of ∼377 MPa and ∼0.68%, respectively. Further, by applying voltages of up to ±40 V the membranes are electrostatically actuated and deflected by up to ∼1.7 µm, as determined via in situ AFM measurements. A simple electrostatic model is presented that describes the deflection of the membrane as a function of the applied voltage very well.
Multimodal Operando Analysis of Lithium Sulfur Multilayer Pouch Cells: An In‐Depth Investigation on Cell Component Design and Performance
Authors: Müller Rafael , Boenke Tom , Dörfler Susanne , Abendroth Thomas , Härtel Paul , Althues Holger , Kaskel Stefan , Kardjilov Nikolay , Markötter Henning , Sintschuk Michael , Hilger André , Manke Ingo , Risse Sebastian 
Published: January 2025

AbstractThis study presents an innovative operando analysis of lithium‐sulfur (Li/S) multilayer pouch cells, employing a combination of lab‐source and synchrotron x‐ray imaging to investigate sulfur crystallite dissolution and lithium dendrite formation. By integrating advanced X‐ray imaging, impedance spectroscopy, and simultaneous monitoring of temperature and pressure, the research uncovers critical insights into the behavior of active and inactive cell components. The analysis reveals significant degradation increments, primarily driven by side product accumulation and the deterioration of lithium microstructures, which contribute to performance loss over cycling. Additionally, temperature distribution analysis shows a strong correlation between joule heating, polarization resistance, and the observed endothermic processes during crystallization. These findings provide a comprehensive understanding of the mechanistic processes within industrially relevant pouch cells, highlighting opportunities for optimizing Li/S cell designs and advancing high‐energy‐density battery systems for commercial applications.
In Situ Monitoring of Dynamic Adsorption‐Induced Interfacial Buffering Toward Highly Stable Zinc Metal Batteries
Authors: Duan An , Luo Sha , Tang Yuyang , Feng Yu , Li Ming , Zhang Bao , Sun Wei 
Published: January 2025

AbstractElectrolyte regulation and electrode/electrolyte interface optimization are recognized as crucial strategies for mitigating parasitic reactions and enhancing zinc plating/stripping in zinc metal batteries. Despite their established importance, the underlying mechanisms of interface behavior and optimization remain elusive, especially in the absence of robust experimental characterization of adsorption‐dominated approaches. Herein, in situ monitoring of interfacial adsorption effect is presented, employing a theoretically screened cyclen‐based additive. The dynamic adsorption behavior in response to alternating electric fields is identified as pivotal in regulating the metal‐electrolyte interfaces, as evidenced by a combination of in situ electrochemical quartz crystal microbalance (eQCM) measurements and constant‐potential molecular dynamics simulation. Such dynamic adsorption provides a robust pH buffering effect at the zinc‐metal anode interface, facilitating orderly and uniform zinc plating/stripping. Consequently, the electrochemical performance of zinc‐based half cells and full cells is markedly enhanced. The findings offer comprehensive insights into the strategic development of functional electrolyte additives for aqueous zinc metal batteries.
Elevated Practical Volumetric Density and Cyclic Durability of Selenium Cathodes by Powder Microspheroidization and Kilogram‐Scale Atomic Layer Deposition Techniques
Authors: Li Yi , Zhu Jianhui , Qi Yuruo , Xu Maowen , Jiang Jian 
Published: January 2025

AbstractPractical usage of high‐energy chalcogen cathodes, typically like selenium (Se), is plagued by compromised volumetric energy density and cyclic lifespan in pouch cells, due to the low cathode compactness and continuous Li2Sen shutting issues. Inspired by classic close‐packing theories and self‐limiting configurations, we propose to construct high‐tap‐density microsphere cathodes made of Se nano yolks and N‐rich carbon (NC)‐TiO2 shells via a kilogram‐scale atomic layer deposition (ALD) technique. The utilized particle microspheroidization strategy makes powders approach the Max. theoretical volume fraction of 0.64, achieving intrinsically high tap density (2.06 g cm−3) and large areal Se loading ratio beyond 8.4 mg cm−2 after slurry coating. A molecular‐engineered oxidative polypyrrole (O‐PPy) layer covered on Se surfaces plays an indispensable role in guaranteeing smooth ALD implementation. The formed robust NC‐TiO2 microreactors solidly confining Se actives in spatial regions help to expedite Li2Sen phase conversions, rendering cathodes with a remarkable capacity of 502 mAh g−1 (0.5C) and far lessened capacity decay in all cycling. Their assembled pouch cells are ∼20% thinner than those of random‐shaped counterparts, showing an exceptionally high Ev value over 1158.3 Wh L−1. This work may propel the advent of Li‐chalcogen cells with unprecedented volumetric energy densities for near‐future applications.
Intercropping alfalfa during almond orchard establishment reduces winter soil nitrogen and water losses, provides on‐farm revenue
Authors: Thao Touyee , Begna Sultan , Hale Lauren , Bali Khaled M. , Wang Dong , Gao Suduan 
Published: January 2025

AbstractThe ecosystem benefits linked to intercropping and diversified agroecosystems is an area with increasing research interest, particularly in sustainable food production and farm resilience to extreme climate variability. Interrow cropping of alfalfa (Medicago sativa L.) in almond [Prunus dulcis (Mill.) D. A. Webb] orchards during the 3–4 non‐bearing, establishment years has potential to advance sustainable intensification in agricultural regions such as the Central Valley of California. In this study we evaluated ecosystem benefits linked to this intercropped agroecosystem in contrast to conventional almond systems with interrow spaces maintained bare. From Winter 2023 to Spring 2024 (157 days), we modeled soil hydrological properties (HYDRUS‐1D) and quantified soil nitrogen using various approaches. Simulation from HYDRUS revealed that winter soil evaporative loss was most substantial for a flood‐irrigated bare‐soil control (208.1 mm) and lowest for the alfalfa intercropped interrow (59.2 mm). Estimated soil water storage was lowest in the alfalfa intercropped interrow and highest for bare‐soil controls, indicating continuous plant water uptake throughout the winter period when almond trees are dormant. Winter soil N loss measured using suction lysimeters, ion exchange soil resins traps, and soil sampling (0–120 cm) indicated that N leaching was greatest in the bare‐soil interrow spaces and lowest for alfalfa intercropped treatment. The utilization of free winter inputs, such as rainwater and slow‐release mineralized N from dairy manure compost, translated to a 2.22 tonne ha−1 alfalfa yield and equated to a $500 ha−1 gross revenue for the first alfalfa cutting. Overall, the preliminary ecosystem benefits observed in this unique alfalfa–almond intercropped agroecosystem were attributed to augmentation in farm resource use efficiency and revenues generated during the winter season.
Budesonide, Added to PTCy‐Based Regimen, for Prevention of Acute GI GVHD After Allogeneic Stem Cell Transplantation
Authors: Kongtim Piyanuch , Chumnumsiriwath Piyatida , Vittayawacharin Pongthep , Jeyakumar Deepa , Lee Benjamin J. , Doh Jean , Griffin Shawn P. , Van Etten Richard A. , Ciurea Stefan 
Published: January 2025

ABSTRACTOral budesonide exerts local effects with negligible systemic glucocorticoid activity, due to rapid first‐pass metabolism, therefore, could potentially be efficacious in preventing gastrointestinal (GI) acute GVHD (aGVHD). We explored the use of budesonide, added to posttransplant cyclophosphamide (PTCy), tacrolimus, and mycophenolate mofetil, for prevention of GI aGVHD after allogeneic hematopoietic stem cell transplantation (AHSCT) in a prospective observational study and treated 80 patients with a median age of 53 years (range 19–74). Results were compared with a publicly available CIBMTR dataset of 646 patients who received PTCy‐based GVHD prophylaxis (CIBMTR Study # GV17‐02) (control). Cumulative incidence (CI) of 3‐month grade 2–4 and grade 3–4 aGVHD in the budesonide and control groups were 3.8% vs. 34.4% (p < 0.001) and 1.3% vs. 9.8% (p = 0.029), respectively. One‐year GRFS (70.5% vs. 31.5%, p < 0.001), PFS (73.4% vs. 52.8%, p = 0.003), and OS (80.1% vs. 64.2%, p = 0.038) were significantly higher in the budesonide group compared with control group. Propensity score‐adjusted analyses showed that the addition of budesonide significantly decreased risk of aGVHD grade 2–4 (HR 0.29, p < 0.001), grade 3–4 (HR 0.12, p = 0.045), and cGVHD (HR 0.22, p < 0.001), which resulted in better GRFS (HR 0.38, p < 0.001), PFS (HR 0.58, p = 0.012), and OS (HR 0.72, p = 0.044). Similar results were found when using propensity score‐matched analysis restricted to recipients of haploidentical transplantation. In conclusion, addition of budesonide to PTCy‐based GVHD prophylaxis is safe and effective in preventing severe acute GI GVHD with significantly improved GRFS. These results could facilitate transition to peripheral blood grafts for all allogeneic transplant recipients.