bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dosimetric impact of contour editing on CT and MRI deep‐learning autosegmentation for brain OARs
Authors: Alzahrani Nouf M. , Henry Ann M. , Clark Anna K. , Al‐Qaisieh Bashar M. , Murray Louise J. , Nix Michael G. 
Published: April 2024

AbstractPurposeTo establish the clinical applicability of deep‐learning organ‐at‐risk autocontouring models (DL‐AC) for brain radiotherapy. The dosimetric impact of contour editing, prior to model training, on performance was evaluated for both CT and MRI‐based models. The correlation between geometric and dosimetric measures was also investigated to establish whether dosimetric assessment is required for clinical validation.MethodCT and MRI‐based deep learning autosegmentation models were trained using edited and unedited clinical contours. Autosegmentations were dosimetrically compared to gold standard contours for a test cohort. D1%, D5%, D50%, and maximum dose were used as clinically relevant dosimetric measures. The statistical significance of dosimetric differences between the gold standard and autocontours was established using paired Student's t‐tests. Clinically significant cases were identified via dosimetric headroom to the OAR tolerance. Pearson's Correlations were used to investigate the relationship between geometric measures and absolute percentage dose changes for each autosegmentation model.ResultsExcept for the right orbit, when delineated using MRI models, the dosimetric statistical analysis revealed no superior model in terms of the dosimetric accuracy between the CT DL‐AC models or between the MRI DL‐AC for any investigated brain OARs. The number of patients where the clinical significance threshold was exceeded was higher for the optic chiasm D1% than other OARs, for all autosegmentation models. A weak correlation was consistently observed between the outcomes of dosimetric and geometric evaluations.ConclusionsEditing contours before training the DL‐AC model had no significant impact on dosimetry. The geometric test metrics were inadequate to estimate the impact of contour inaccuracies on dose. Accordingly, dosimetric analysis is needed to evaluate the clinical applicability of DL‐AC models in the brain.
A Universal Biomineralization‐Like Interfacial‐Confined Strategy Enables Practicable, Meter‐Scale, Transmittance‐Adjustable, Highly‐Ordered, Photothermal‐Capable, 2D Conducting Polymers
Authors: Wei Mengzhen , Zhu Yucheng , Wang Xusheng , Ma Xinlei , Ma Hui , Du Yuhang , Chen Ruoqi , Ji Junhui , Xue Mianqi 
Published: April 2024

AbstractConducting polymers (CPs) encompass various cutting‐edge fields owing to their combination of polymer and conducting properties. However, the mismatch between the polymer growth process and the carrier mobility design leads to poor material and device consistency, and insufficient long‐term device stability, thus hindering the practical application of CPs. Although 2D construction has been explored to address these challenges, it typically leads to materials instability and lacks methods for large‐scale synthesis, making it unsuitable for many application scenarios. Here a universal biomineralization‐like strategy relying on the joint impaction of hydrogen‐bond and gravity for large‐scale fabrication of 2D CPs is developed. As‐fabricated meter‐scale Polypyrrole films exhibit high orderliness and can be assembled into multilayers, allowing for adjustable thickness and transparency. Notably, these films demonstrate exceptional photothermal properties and remarkable long‐term stability, as their surface temperature can reach 140 °C when irradiated with an 808 nm laser at 0.7 W cm−2, with almost no attenuation after 170 days. Furthermore, under sunlight, the temperature can reach nearly 100 °C, showcasing significant potential in smart building and energy management applications. Importantly, this strategy can be extended to the 2D design of numerous light organic compounds, thus opening up possibilities for their practical applications.
A Novel Carbazolophane: A Comparison of the Performance of Two Planar Chiral CP‐TADF Emitters
Authors: Seibert Jasmin , Xu Yan , Hafeez Hassan , Podlech Joachim , Favereau Ludovic , Spuling Eduard , Waldhelm Charlotte , Nieger Martin , Fuhr Olaf , Hassan Zahid , Crassous Jeanne , Samuel Ifor D. W. , Zysman‐Colman Eli , Bräse Stefan 
Published: April 2024

AbstractThe prototypical example of a (cyclo)phane, [2.2]paracyclophane (PCP), has proven to be a versatile stereogenic moiety within the design of circularly polarized thermally activated delayed fluorescence (CP‐TADF) emitters; however, the exploration of other cyclophanes within CP‐TADF emitter design has been largely neglected. Here, a comparative study of the photophysical and optoelectronic properties of two cyclophane emitters, (1,7)tBuCzpPhTrz and its isomer (1,4)tBuCzpPhTrz, is presented. The carbazolophane‐triazine compound (1,7)tBuCzpPhTrz, obtained via an unprecedented intramolecular rearrangement, is the first example of a planar chiral TADF emitter deviating from the PCP scaffold. Significant geometrical change of the enclosed carbazole in (1,7)tBuCzp results in an attenuation of the donor strength, while the merits of rigidity and steric bulk remain. In particular, the full width at half maximum (FWHM) of the photoluminescence spectrum in toluene of (1,7)tBuCzpPhTrz is reduced by 34% and blue‐shifted by 20 nm compared to that of (1,4)tBuCzpPhTrz. In doped films, the compounds reach high photoluminescence quantum yields (ΦPL) of 91 and 81%, respectively. The chiroptical properties reveal dissymmetry factors |gPL| of up to 5 × 10−4. These results demonstrate the impact of the cyclophane for the development of CP‐TADF materials and add to the currently limited scope of available planar chiral donors.
Double‐Layered Hollow Mesoporous Cuprous Oxide Nanoparticles for Double Drug Sequential Therapy of Tumors
Authors: Li Zongheng , Yang Jing , Ren Bin , Fan Qingdeng , Huang Lin , Guo Shuai , Zhou RuiLong , Chen Sijin , Feng Jie , Yan Chenggong , Chen Xiaoyuan , Shen Zheyu 
Published: April 2024

AbstractCancer stem cells (CSCs) are one of the determinants of tumor heterogeneity and are characterized by self‐renewal, high tumorigenicity, invasiveness, and resistance to various therapies. To overcome the resistance of traditional tumor therapies resulting from CSCs, a strategy of double drug sequential therapy (DDST) for CSC‐enriched tumors is proposed in this study and is realized utilizing the developed double‐layered hollow mesoporous cuprous oxide nanoparticles (DL‐HMCONs). The high drug‐loading contents of camptothecin (CPT) and all‐trans retinoic acid (ATRA) demonstrate that the DL‐HMCON can be used as a generic drug delivery system. ATRA and CPT can be sequentially loaded in and released from CPT3@ATRA3@DL‐HMCON@HA. The DDST mechanisms of CPT3@ATRA3@DL‐HMCON@HA for CSC‐containing tumors are demonstrated as follows: 1) the first release of ATRA from the outer layer induces differentiation from CSCs with high drug resistance to non‐CSCs with low drug resistance; 2) the second release of CPT from the inner layer causes apoptosis of non‐CSCs; and 3) the third release of Cu+ from DL‐HMCON itself triggers the Fenton‐like reaction and glutathione depletion, resulting in ferroptosis of non‐CSCs. This CPT3@ATRA3@DL‐HMCON@HA is verified to possess high DDST efficacy for CSC‐enriched tumors with high biosafety.
Multilaminate Energy Storage Films from Entropy‐Driven Self‐Assembled Supramolecular Nanocomposites
Authors: Li He , Vargo Emma , Xie Zongliang , Ma Le , Pieters Priscilla F. , Shelton Steve W. , Alivisatos Armand Paul , Xu Ting , Liu Yi 
Published: April 2024

AbstractComposite materials comprising polymers and inorganic nanoparticles (NPs) are promising for energy storage applications, though challenges in controlling NP dispersion often result in performance bottlenecks. Realizing nanocomposites with controlled NP locations and distributions within polymer microdomains is highly desirable for improving energy storage capabilities but is a persistent challenge, impeding the in‐depth understanding of the structure–performance relationship. In this study, a facile entropy‐driven self‐assembly approach is employed to fabricate block copolymer‐based supramolecular nanocomposite films with highly ordered lamellar structures, which are then used in electrostatic film capacitors. The oriented interfacial barriers and well‐distributed inorganic NPs within the self‐assembled multilaminate nanocomposites effectively suppress leakage current and mitigate the risk of breakdown, showing superior dielectric strength compared to their disordered counterparts. Consequently, the lamellar nanocomposite films with optimized composition exhibit high energy efficiency (>90% at 650 MV m−1), along with remarkable energy density and power density. Moreover, finite element simulations and statistical modeling have provided theoretical insights into the impact of the lamellar structure on electrical conduction, electric field distribution, and electrical tree propagation. This work marks a significant advancement in the design of organic–inorganic hybrids for energy storage, establishing a well‐defined correlation between microstructure and performance.
Self‐Encapsulation of High‐Entropy Alloy Nanoparticles inside Carbonized Wood for Highly Durable Electrocatalysis
Authors: Wang Yaoxing , Zhang Yang , Xing Pengyu , Li Xueqi , Du Qiuyu , Fan Xueqin , Cai Zhibin , Yin Ran , Yao Yonggang , Gan Wentao 
Published: April 2024

AbstractHigh‐entropy alloy nanoparticles (HEAs) show great potential in emerging electrocatalysis due to their combination and optimization of multiple elements. However, synthesized HEAs often exhibit a weak interface with the conductive substrate, hindering their applications in long‐term catalysis and energy conversion. Herein, a highly active and durable electrocatalyst composed of quinary HEAs (PtNiCoFeCu) encapsulated inside the activated carbonized wood (ACW) is reported. The self‐encapsulation of HEAs is achieved during Joule heating synthesis (2060 K, 2 s) where HEAs naturally nucleate at the defect sites. In the meantime, HEAs catalyze the deposition of mobile carbon atoms to form a protective few‐layer carbon shell during the rapid quenching process, thus remarkably strengthening the interface stability between HEAs and ACW. As a result, the HEAs@ACW shows not only favorable activity with an overpotential of 7 mV at 10 mA cm−2 for hydrogen evolution but also negligible attenuation during a 500 h stability test, which is superior to most reported electrocatalysts. The design of self‐encapsulated HEAs inside ACW provides a critical strategy to enhance both activity and stability, which is also applicable to many other energy conversion technologies.
The Role of Solution Aggregation Property toward High‐Efficiency Non‐Fullerene Organic Photovoltaic Cells
Authors: Xu Lei , Li Sunsun , Zhao Wenchao , Xiong Yaomeng , Yu Jinfeng , Qin Jinzhao , Wang Gang , Zhang Rui , Zhang Tao , Mu Zhen , Zhao Jingjing , Zhang Yuyang , Zhang Shaoqing , Kuvondikov Vakhobjon , Zakhidov Erkin , Peng Qiming , Wang Nana , Xing Guichuan , Gao Feng , Hou Jianhui , Huang Wei , Wang Jianpu 
Published: April 2024

AbstractIn organic photovoltaic cells, the solution‐aggregation effect (SAE) is long considered a critical factor in achieving high power‐conversion efficiencies for polymer donor (PD)/non‐fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D‐benzodithiophene‐based PDs and acceptor–donor–acceptor‐type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well‐known polymer‐templated fibrillar network structures and superior PCEs. With the weakening of PDs’ aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems.
Degradation‐Based Protein Profiling: A Case Study of Celastrol
Authors: Ni Zhihao , Shi Yi , Liu Qianlong , Wang Liguo , Sun Xiuyun , Rao Yu 
Published: April 2024

AbstractNatural products, while valuable for drug discovery, encounter limitations like uncertainty in targets and toxicity. As an important active ingredient in traditional Chinese medicine, celastrol exhibits a wide range of biological activities, yet its mechanism remains unclear. In this study, they introduced an innovative “Degradation‐based protein profiling (DBPP)” strategy, which combined PROteolysis TArgeting Chimeras (PROTAC) technology with quantitative proteomics and Immunoprecipitation‐Mass Spectrometry (IP‐MS) techniques, to identify multiple targets of natural products using a toolbox of degraders. Taking celastrol as an example, they successfully identified its known targets, including inhibitor of nuclear factor kappa B kinase subunit beta (IKKβ), phosphatidylinositol‐4,5‐bisphosphate 3‐kinase catalytic subunit alpha (PI3Kα), and cellular inhibitor of PP2A (CIP2A), as well as potential new targets such as checkpoint kinase 1 (CHK1), O‐GlcNAcase (OGA), and DNA excision repair protein ERCC‐6‐like (ERCC6L). Furthermore, the first glycosidase degrader is developed in this work. Finally, by employing a mixed PROTAC toolbox in quantitative proteomics, they also achieved multi‐target identification of celastrol, significantly reducing costs while improving efficiency. Taken together, they believe that the DBPP strategy can complement existing target identification strategies, thereby facilitating the rapid advancement of the pharmaceutical field.
A Self‐Assembled MOF‐Escherichia Coli Hybrid System for Light‐Driven Fuels and Valuable Chemicals Synthesis
Authors: Li Jialu , Shen Junfeng , Hou Tianfeng , Tang Hongting , Zeng Cuiping , Xiao Kemeng , Hou Yanping , Wang Bo 
Published: April 2024

AbstractThe development of semi‐artificial photosynthetic systems, which integrate metal–organic frameworks (MOFs) with industrial microbial cell factories for light‐driven synthesis of fuels and valuable chemicals, represents a highly promising avenue for both research advancements and practical applications. In this study, an MOF (PCN‐222) utilizing racemic‐(4‐carboxyphenyl) porphyrin and zirconium chloride (ZrCl4) as primary constituents is synthesized. Employing a self‐assembly process, a hybrid system is constructed, integrating engineered Escherichia coli (E. coli) to investigate light‐driven hydrogen and lysine production. These results demonstrate that the light‐irradiated biohybrid system efficiently produce H2 with a quantum efficiency of 0.75% under full spectrum illumination, the elevated intracellular reducing power NADPH is also observed. By optimizing the conditions, the biohybrid system achieves a maximum lysine production of 18.25 mg L−1, surpassing that of pure bacteria by 332%. Further investigations into interfacial electron transfer mechanisms reveals that PCN‐222 efficiently captures light and facilitates the transfer of photo‐generated electrons into E. coli cells. It is proposed that the interfacial energy transfer process is mediated by riboflavin, with facilitation by secreted small organic acids acting as hole scavengers for PCN‐222. This study establishes a crucial foundation for future research into the light‐driven biomanufacturing using E. coli‐based hybrid systems.
Endogenous Melanin and Hydrogen‐Based Specific Activated Theranostics Nanoagents: A Novel Multi‐Treatment Paradigm for Rheumatoid Arthritis
Authors: Chen Lin , Zhao Mingxin , Kang Weiwei , Yu Lujie , Zhang Chongqing , Wu Shutong , Song Xiaorui , Zhao Keqi , Liu Pengmin , Liu Qin , Dai Rong , Zheng Ziliang , Zhang Ruiping 
Published: April 2024

AbstractRheumatoid arthritis (RA) is a systemic autoimmune disorder characterized by excessive proliferation of rheumatoid arthritis synovial fibroblasts (RASFs) and accumulation of inflammatory cytokines. Exploring the suppression of RASFs and modulation of the RA microenvironment is considered a comprehensive strategy for RA. In this work, specifically activated nanoagents (MAHI NGs) based on the hypoxic and weakly acidic RA microenvironment are developed to achieve a second near‐infrared fluorescence (NIR‐II FL)/photoacoustic (PA) dual‐model imaging‐guided multi‐treatment. Due to optimal size, the MAHI NGs passively accumulate in the diseased joint region and undergo rapid responsive degradation, precisely releasing functionalized components: endogenous melanin‐nanoparticles (MNPs), hydrogen gas (H2), and indocyanine green (ICG). The released MNPs play a crucial role in ablating RASFs within the RA microenvironment through photothermal therapy (PTT) guided by accurate PA imaging. However, the regional hyperthermia generated by PTT may exacerbate reactive oxygen species (ROS) production and inflammatory response following cell lysis. Remarkably, under the acidic microenvironment, the controlled release of H2 exhibits precise synergistic antioxidant and anti‐inflammatory effects with MNPs. Moreover, the ICG, the second near‐infrared dye currently approved for clinical use, possesses excellent NIR‐II FL imaging properties that facilitate the diagnosis of deep tissue diseases and provide the right time‐point for PTT.
Lateral Heterostructure Formed by Highly Thermally Conductive Fluorinated Graphene for Efficient Device Thermal Management
Authors: Wang Fanfan , Liu Zexin , Li Jinfeng , Huang Jian , Fang Li , Wang Xiaofeng , Dai Ruiwen , Li Kangyong , Zhang Rong , Yang Xiaoran , Yue Yue , Wang Zhiqiang , Gao Yuan , Yang Kai , Zhang Lifu , Xin Guoqing 
Published: April 2024

AbstractThe continued miniaturization of chips demands highly thermally conductive materials and effective thermal management strategies. Particularly, the high‐field transport of the devices built with 2D materials is limited by self‐heating. Here a systematic control of heat flow in single‐side fluorinated graphene (FG) with varying degrees of fluorination is reported, revealing a superior room‐temperature thermal conductivity as high as 128 W m−1 K−1. Monolayer graphene/FG lateral heterostructures with seamless junctions are approached for device fabrication. Efficient in‐plane heat removal paths from graphene channel to side FG are created, contributing significant reduction of the channel peak temperature and improvement in the current‐carrying capability and power density. Molecular dynamics simulations indicate that the interfacial thermal conductance of the heterostructure is facilitated by the high degree of overlap in the phonon vibrational spectra. The findings offer novel design insights for efficient heat dissipation in micro‐ and nanoelectronic devices.
Activation and Purification of ß‐Glucocerebrosidase by Exploiting its Transporter LIMP‐2 – Implications for Novel Treatment Strategies in Gaucher's and Parkinson's Disease
Authors: Dobert Jan Philipp , Bub Simon , Mächtel Rebecca , Januliene Dovile , Steger Lisa , Regensburger Martin , Wilfling Sibylle , Chen Jia‐Xuan , Dejung Mario , Plötz Sonja , Hehr Ute , Moeller Arne , Arnold Philipp , Zunke Friederike 
Published: April 2024

AbstractGenetic variants of GBA1 can cause the lysosomal storage disorder Gaucher disease and are among the highest genetic risk factors for Parkinson's disease (PD). GBA1 encodes the lysosomal enzyme beta‐glucocerebrosidase (GCase), which orchestrates the degradation of glucosylceramide (GluCer) in the lysosome. Recent studies have shown that GluCer accelerates α‐synuclein aggregation, exposing GCase deficiency as a major risk factor in PD pathology and as a promising target for treatment. This study investigates the interaction of GCase and three disease‐associated variants (p.E326K, p.N370S, p.L444P) with their transporter, the lysosomal integral membrane protein 2 (LIMP‐2). Overexpression of LIMP‐2 in HEK 293T cells boosts lysosomal abundance of wt, E326K, and N370S GCase and increases/rescues enzymatic activity of the wt and E326K variant. Using a novel purification approach, co‐purification of untagged wt, E326K, and N370S GCase in complex with His‐tagged LIMP‐2 from cell supernatant of HEK 293F cells is achieved, confirming functional binding and trafficking for these variants. Furthermore, a single helix in the LIMP‐2 ectodomain is exploited to design a lysosome‐targeted peptide that enhances lysosomal GCase activity in PD patient‐derived and control fibroblasts. These findings reveal LIMP‐2 as an allosteric activator of GCase, suggesting a possible therapeutic potential of targeting this interaction.
Boosting the Faradaic Efficiency of Br−‐Mediated Photoelectrochemical Epoxidation by Local Acidity on α‐Fe2O3
Authors: Duan Meng‐Yu , Tang Dao‐Jian , Yang Jie , Yang Si‐Peng , Deng Chao‐Yuan , Zhao Yu‐Kun , Li Ji‐Kun , Zhang Yu‐Chao , Chen Chun‐Cheng , Zhao Jin‐Cai 
Published: April 2024

AbstractThe redox mediated photoelectrochemical (PEC) or electrochemical (EC) alkene oxidation process is a promising method to produce high value‐added epoxides. However, due to the competitive reaction of water oxidation and overoxidation of the mediator, the utilization of the electricity is far below the ideal value, where the loss of epoxidation's faradaic efficiency (FE) is ≈50%. In this study, a Br−/HOBr‐mediated method is developed to achieve a near‐quantitative selectivity and ≈100% FE of styrene oxide on α‐Fe2O3, in which low concentration of Br− as mediator and locally generated acidic micro‐environment work together to produce the higher active HOBr species. A variety of styrene derivatives are investigated with satisfied epoxidation performance. Based on the analysis of local pH‐dependent epoxidation FE and products distribution, the study further verified that HOBr serves as the true active mediator to generate the bromohydrin intermediate. It is believed that this strategy can greatly overcome the limitation of epoxidation FE to enable future industrial applications.
Asymmetric Cu(I)─W Dual‐Atomic Sites Enable C─C Coupling for Selective Photocatalytic CO2 Reduction to C2H4
Authors: Mao Yuyin , Zhang Minghui , Zhai Guangyao , Si Shenghe , Liu Dong , Song Kepeng , Liu Yuanyuan , Wang Zeyan , Zheng Zhaoke , Wang Peng , Dai Ying , Cheng Hefeng , Huang Baibiao 
Published: April 2024

AbstractSolar‐driven CO2 reduction into value‐added C2+ chemical fuels, such as C2H4, is promising in meeting the carbon‐neutral future, yet the performance is usually hindered by the high energy barrier of the C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms‐modified W18O49 nanowires (Cu1/W18O49) photocatalyst with asymmetric Cu─W dual sites is reported for selective photocatalytic CO2 reduction to C2H4. The interconversion between W(V) and W(VI) in W18O49 ensures the stability of Cu(I) during the photocatalytic process. Under light irradiation, the optimal Cu1/W18O49 (3.6‐Cu1/W18O49) catalyst exhibits concurrent high activity and selectivity toward C2H4 production, reaching a corresponding yield rate of 4.9 µmol g−1 h−1 and selectivity as high as 72.8%, respectively. Combined in situ spectroscopies and computational calculations reveal that Cu(I) single atoms stabilize the *CO intermediate, and the asymmetric Cu─W dual sites effectively reduce the energy barrier for the C─C coupling of two neighboring CO intermediates, enabling the highly selective C2H4 generation from CO2 photoreduction. This work demonstrates leveraging stabilized atomically‐dispersed Cu(I) in asymmetric dual‐sites for selective CO2‐to‐C2H4 conversion and can provide new insight into photocatalytic CO2 reduction to other targeted C2+ products through rational construction of active sites for C─C coupling.