bluuebunny/crossref_metadata_2025 huggingface dataset:
High‐Dissolution Mechanism of Ti–48Al–2Cr–2Nb Alloy in Electrochemical Machining from a Nonlinear Dynamic Perspective
Authors: Lin Rong Lian , Li Wen Yuan , Li Ling , Liao Cui Jiao
Published: April 2024

High‐rate dissolution process of Ti–48Al–2Cr–2Nb alloy in electrochemical machining exhibits strong nonlinear dynamic characteristics, but the quantitative relationship between these nonlinear characteristics and surface topography, as well as the electro‐dissolution mechanism, is unknown. Therefore, the fractal and recursive features of dissolution behavior and quantitative characterization of the dissolved surface topography were investigated. Additionally, an electro‐dissolution mechanism model in electrochemical machining process was presented. Applying a higher potential of 11 V can enhance the stability of the electrochemical system, resulting in a smoother and uniform surface. The saturation correlation dimension, surface roughness, and integral area of lacunarity initially decrease before increasing with higher electrolytic pressure, while laminarity and determinism show an initial increase followed by a decrease. These five characteristic parameters reach their optimal values at an electrolyte pressure of 0.4 MPa, indicating that achieving a stable and deterministic electrochemical system is crucial for obtaining a uniform smooth surface. These nonlinear dynamic characteristic parameters can be considered as in‐situ monitoring parameters for surface quality in ECM. The anodic dissolution process comprises three stages: initial passive film dissolution and breakdown, rapid dissolving with surface coarsening, and stable dissolving with polishing.
Parameters Optimization of Active Flexible Tool‐Assisted Shear Thickening Polishing Method for Concave Surface
Authors: Chen Xinyu , Cai Jingyu , Shao Lanying , Lyu Binghai
Published: April 2024

An innovative approach, active flexible tool‐assisted shear thickening polishing (AFT‐STP), is introduced to overcome the limitations of low efficiency involved in the STP process of the concave surface. The principle and characteristics of AFT‐STP are presented, accompanied by the design of a flexible tool structure and the creation of an experimental setup. Utilizing the Taguchi method, experiments are planned and results are assessed via the signal‐to‐noise ratio to optimize process parameters. A variance analysis is then used to ascertain the relative influence of four key parameters—polishing speed, polishing gap, abrasive particle size, and abrasive concentration on the polishing performance of quartz glass in STP. Under the optimal parameters, a concave quartz glass workpiece with diameter Ø 20 mm and curvature radius 488 mm is polished, the average surface roughness Sa of the five measuring points on the surface decreases from 142.18 ± 8.63 (Avg. ± Std.) nm to 5.34 ± 1.16 nm in 45 min with MRR 57.3 nm min−1, and the surface defects of the processing area are completely removed, leaving only minor pits. The results show that the AFT‐STP is an effective method for high‐quality polishing of concave surfaces.
Cyclic R‐Curve Measurements for Structural Metallic Alloys
Authors: Patriarca Luca , D’Andrea Antonio , Cova Matteo , Rusnati Lorenzo , Beretta Stefano
Published: April 2024

Fractures nucleated from defects and subjected to cyclic loading can experience propagation for a range of stress intensity factor ΔK well below the so‐called long crack threshold. This phenomenon is attributed to the development of crack closure mechanisms which may differ from those observed in laboratory tests conducted in accordance with current standards. Cracks originating from material defects require a specific degree of extension to develop the plastic wake, thus achieving a stabilized condition called the long crack threshold. However, in certain materials, this stabilization length can extend up to several millimeters, effectively encompassing a significant portion of the component's fatigue life. Therefore, understanding and quantifying the development of ΔKth with crack extension is important for implementing a reliable assessment procedure based on the fracture mechanics theory. Herein, R‐curve measurements are presented for five distinct structural metallic alloys widely used in various industrial applications. Additionally, the impact of load ratio is investigated, providing a comprehensive analysis of fatigue crack resistance in terms of the R‐curve concept. This study underscores the necessity of ruling new experimental techniques to measure and implement the long crack threshold, thereby ensuring the development of a reliable and robust framework for fatigue assessment.
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

Conducting 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

The 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

Cancer 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

Composite 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

High‐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

In 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

Natural 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

The 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

Rheumatoid 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

The 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

Genetic 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

The 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

Solar‐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.
Entropy Engineering Constrain Phase Transitions Enable Ultralong‐life Prussian Blue Analogs Cathodes
Authors: Lei Yuhao , Wang Shiyong , Zhao Lin , Li Changping , Wang Gang , Qiu Jieshan
Published: April 2024

Prussian blue analogs (PBAs) are considered as one of the most potential electrode materials in capacitive deionization (CDI) due to their unique 3D framework structure. However, their practical applications suffer from low desalination capacity and poor cyclic stability. Here, an entropy engineering strategy is proposed that incorporates high‐entropy (HE) concept into PBAs to address the unfavorable multistage phase transitions during CDI desalination. By introducing five or more metals, which share N coordination site, high‐entropy hexacyanoferrate (HE‐HCF) is constructed, thereby increasing the configurational entropy of the system to above 1.5R and placing it into the high‐entropy category. As a result, the developed HE‐HCF demonstrates remarkable cycling performance, with a capacity retention rate of over 97% after undergoing 350 ultralong‐life cycles of adsorption/desorption. Additionally, it exhibits a high desalination capacity of 77.24 mg g−1 at 1.2 V. Structural characterization and theoretical calculation reveal that high configurational entropy not only helps to restrain phase transition and strengthen structural stability, but also optimizes Na+ ions diffusion path and energy barrier, accelerates reaction kinetics and thus improves performance. This research introduces a new approach for designing electrodes with high performance, low cost, and long‐lasting durability for capacitive deionization applications.
Small Molecule Regulatory Strategy for Inorganic Perovskite Solar Cells with 368 mV of VOC Deficit and its Application in Tandem Devices
Authors: Wang Sanlong , Sun Hongrui , Wang Pengyang , Ge Xin , Li Yucheng , Li Diannan , Huang Qian , Du Xiaona , Zhao Ying , Zhang Xiaodan
Published: April 2024

Tandem solar cells combining perovskite and silicon have witnessed rapid development in recent years. However, the top cell, utilizing wide‐bandgap perovskite as absorbers generally suffer significant open‐circuit voltage (VOC) deficit, particularly for inorganic perovskite, which poses a considerable obstacle to enhancing the power conversion efficiency (PCE). Here, a modulation strategy by using 2,6‐pyridinedicarboxamide (PC), the crystallization kinetics of inorganic perovskite film can be effectively regulated, specifically manifested as a relatively longer annealing time in the air, resulting in sufficient growth for the inorganic perovskite grains. Additionally, PC can effectively in situ passivate uncoordinated Pb2+, suppressing the non‐radiative recombination of charge carriers. Eventually, a record PCE of 22.07% is achieved based on n–i–p inorganic perovskite solar cells (IPSCs), which also demonstrate the highest VOC above 1.34 V (1.71 eV of bandgap). More importantly, the unencapsulated IPSCs show enhanced thermal stability and photostability. Furthermore, the n–i–p IPSCs are also applied to inorganic perovskite/silicon tandem solar cells (IPTSCs), a PCE of 27.27% and an impressive VOC of 2.024 V are obtained.
Atomically‐Scattered Active Centers Accelerating Photocatalytic Evolution of Ammonia
Authors: Ran Jingrun , Talebian‐Kiakalaieh Amin , Qiao Shi‐Zhang
Published: April 2024

Photocatalytic N2 reduction to ammonia rises as a cost‐effective, environmentally benign, and efficient route to generate ammonia as a transportable/storable energy carrier and essential fertilizer. Recently, photocatalysts anchored with various atomically scattered active centers (ASACs), such as Ru, Fe, Au, Pt, Cu, Mo, and La, are extensively explored in photocatalytic N2‐to‐ammonia transformation. This review critically summarizes the current achievements in the synthesis of various photocatalyst supports (such as metal oxide, carbon nitride, metal‐organic framework, and covalent organic framework) anchored with the above‐mentioned ASACs for N2 reduction to form ammonia. The synthesis routes, structural/compositional characteristics, and performances of these ASACs anchored photocatalysts are summarized and introduced. Furthermore, the atomic‐scale relationship between the structure/composition and performance of these ASACs anchored photocatalysts is also introduced. The reaction mechanism including the reaction kinetics/thermodynamics, reaction pathways, and charge carrier kinetics, especially those revealed by various state‐of‐art characterization techniques, have been highlighted. This review also outlines the basic principles for the synthesis of novel photocatalysts aimed at ammonia evolution. Finally, the current challenges, opportunities, and future outlooks of ASACs anchored photocatalysts for ammonia evolution are introduced.
Allostatic load, adverse childhood experiences, executive functions, and BMI status in adolescents and young adults
Authors: Prunell‐Castañé Anna , Garolera Maite , Ottino‐González Jonatan , Jurado María Ángeles
Published: April 2024

Objectives

Chronic stress induces preclinical changes in the metabolic, cardiovascular, and immune systems. This phenomenon, known as allostatic load (AL), can impair executive functions (EF), which may be even more affected in individuals with excess weight due to their characteristic inflammatory state and cardiometabolic changes. Adverse childhood experiences (ACEs) contribute to AL and may influence executive functioning presumably via alterations within the hypothalamic–pituitary axis, including epigenetic modifications. We assess the relationship between AL and EF in youth with and without excess weight, and the effect ACEs on executive functioning.

Methods

One hundred eighty‐two adolescents and young adults (85 with normal weight and 97 with overweight/obesity; 10–21 years) were recruited. The estimated AL index included the following: systolic and diastolic blood pressure, glycated hemoglobin, high‐ and low‐density lipoprotein cholesterol, triglycerides, high‐sensitivity C‐reactive protein, fibrinogen, and cortisol. ACEs were measured using the Juvenile Victimization Questionnaire. The neuropsychological evaluation included the assessment of inhibition, working memory, and cognitive flexibility processes.

Results

AL was not significantly associated with executive functioning, and this relationship did not depend on body‐weight status. ACEs, available for 57 of 182 participants, were significantly associated with poorer executive functioning.

Conclusions

Our study shows that AL is not associated with executive functioning in adolescents and young adults. Since the current sample was young, we hypothesize that a longer exposure to AL might be required for its negative effects to surface. Nevertheless, exposure to early adversity seems to be associated with poorer executive functioning in youth.
Different fetal effects on fingers from exposure to phenytoin, phenobarbital, and carbamazepine
Authors: Holmes Lewis B. , Hunt Anne‐Therese
Published: April 2024

Exposure at conception to phenytoin (PHT), phenobarbital (PB), and carbamazepine (CBZ) has been associated with several different effects on the fetus, including hypoplasia of the distal phalanges, dysmorphic facial features, and structural abnormalities such as oral clefts and neural tube defects. One question is whether each of these antiepileptic drugs (AEDs) has the same effects or just similar effects. A systematic examination of the fingers of children exposed at conception to PHT, PB, or CBZ, as monotherapy, has been used to address this question. The findings in the examinations of the fingers of 115 AED‐exposed children (40, PHT; 34, PB; 41, CBZ) and their parents were compared to the findings in 111 age‐ and sex‐matched children and their parents. The evaluations used were both subjective assessments and objective measurements. Shortening and narrowing of the fifth fingernail and an increased frequency of arch patterns in the dermal ridges were more common in PHT‐exposed children. A significant decrease in the length of the nail, but not width, occurred in the PB‐exposed children. Stiffness of the interphalangeal joints was more common in the CBZ‐exposed children. The findings in children exposed to PHT, PB, or CBZ, as monotherapy, showed that all three exposures in early pregnancy affected the fingers, but the effects were not the same. The most striking effects were present in PHT‐exposed children.
Primate conservation: A public issue?
Authors: Cosby Alexandria E. , Andriatsitohaina Bertrand , Archie Raquel , Jules Cora , McGoogan Keriann C. , Persram Maya , Razafitsalama Mamy , Young Arayelle , Steffens Travis S.
Published: April 2024

Nonhuman primates (primates) are one of the most endangered mammalian taxa in the world. In the Global North, primates are considered exotic species and, as such, humans' impact on primate conservation and responsibility to protect primates is often ignored. This view differs from the spectrum of relations and attitudes of humans that live in connection to primates, which can include viewing these animals as culturally/religiously significant, cohabitors of forests, nuisances, or sources of protein. While conservationists argue that primates deserve our protection, the conservation crisis facing primates is rarely framed as a public issue, in contrast to other global crises, such as climate change. However, over half of the world's human population lives within 100 km of primate habitat. Thus, humans and primates share the same environments. We suggest leveraging a holistic approach, such as One Health, that considers the interconnectedness of primates, humans, and their shared environments, through the lens of public anthropology. By approaching primate conservation as an intersectional issue that affects and is affected by humans, researchers and conservationists can identify strategies that simultaneously protect primates and address global inequities that frequently affect people in primate range countries. Reflexive research practices further allow academics to consider the broader impact of their ecological research through means such as publicly accessible dissemination of results, equitable capacity‐building of high‐quality personnel in primate range countries, and social activism. The use of inter‐, multi‐, and transdisciplinary concepts and methodology can address the intersectional challenges associated with implementing ethical and sustainable primate conservation measures.
Hepatic steatosis: Qualitative and quantitative sonographic assessment in comparison to histology
Authors: Tan Zhi Xin , Mehta Bryan , Kusel Kieran , Seow James , Zelesco Marilyn , Abbott Steven , Simons Rebecca , Boardman Glenn , Welman Christopher J. , Ayonrinde Oyekoya T.
Published: April 2024

Introduction

Globally, B‐mode ultrasound is the most common modality used for the diagnosis of hepatic steatosis. We aimed to assess the correlation between qualitative liver ultrasound parameters, attenuation imaging (ATI) and histopathology‐diagnosed steatosis grade obtained from liver biopsy. Our secondary aim was to examine the interobserver variability of qualitative ultrasound features.

Methods

A retrospective cohort study was performed which included adult patients (age ≥ 18 years) who had same‐day liver ultrasound, ATI and liver biopsy for grading hepatic steatosis severity between 2018 and 2022. The qualitative US features for hepatic steatosis were independently scored by three radiologists and interobserver variability was examined. Histologic steatosis grade, ATI and qualitative ultrasound parameters were compared.

Results

Ninety patients were included; 67% female with a median age of 54 (IQR 39–65) years. The radiologist's overall impression had the highest correlation (very strongly correlated) with histologic steatosis grade (r = 0.82, P < 0.001). ATI coefficient and all qualitative ultrasound B‐mode features except for liver echotexture and focal fat sparing were strongly correlated with histologic steatosis grade (r ≥ 0.70, P < 0.001). Most qualitative ultrasound features had good agreement between observers (Kappa statistic 0.61–1.0, P < 0.001), (Kendall coefficient 0.92, P < 0.001).

Conclusion

The examined qualitative ultrasound parameters and ATI had good‐excellent performance for diagnosing clinically significant hepatic steatosis; however, the radiologist's overall impression had the best correlation with histologic steatosis grade. Our findings suggest an ongoing role for qualitative liver ultrasound assessment of hepatic steatosis despite the emergence of newer quantitative measures.
α‐Synuclein seed amplification assay detects Lewy body co‐pathology in autosomal dominant Alzheimer's disease late in the disease course and dependent on Lewy pathology burden
Authors: Levin Johannes , Baiardi Simone , Quadalti Corinne , Rossi Marcello , Mammana Angela , Vöglein Jonathan , Bernhardt Alexander , Perrin Richard J. , Jucker Mathias , Preische Oliver , Hofmann Anna , Höglinger Günter U. , Cairns Nigel J. , Franklin Erin E. , Chrem Patricio , Cruchaga Carlos , Berman Sarah B. , Chhatwal Jasmeer P. , Daniels Alisha , Day Gregory S. , Ryan Natalie S. , Goate Alison M. , Gordon Brian A. , Huey Edward D. , Ibanez Laura , Karch Celeste M. , Lee Jae‐Hong , Llibre‐Guerra Jorge , Lopera Francisco , Masters Colin L. , Morris John C. , Noble James M. , Renton Alan E. , Roh Jee Hoon , Frosch Matthew P. , Keene C. Dirk , McLean Catriona , Sanchez‐Valle Raquel , Schofield Peter R. , Supnet‐Bell Charlene , Xiong Chengjie , Giese Armin , Hansson Oskar , Bateman Randall J. , McDade Eric ,   Dominantly Inherited Alzheimer Network, Parchi Piero
Published: April 2024

INTRODUCTION

Amyloid beta and tau pathology are the hallmarks of sporadic Alzheimer's disease (AD) and autosomal dominant AD (ADAD). However, Lewy body pathology (LBP) is found in ≈ 50% of AD and ADAD brains.

METHODS

Using an α‐synuclein seed amplification assay (SAA) in cerebrospinal fluid (CSF) from asymptomatic (n = 26) and symptomatic (n = 27) ADAD mutation carriers, including 12 with known neuropathology, we investigated the timing of occurrence and prevalence of SAA positive reactivity in ADAD in vivo.

RESULTS

No asymptomatic participant and only 11% (3/27) of the symptomatic patients tested SAA positive. Neuropathology revealed LBP in 10/12 cases, primarily affecting the amygdala or the olfactory areas. In the latter group, only the individual with diffuse LBP reaching the neocortex showed α‐synuclein seeding activity in CSF in vivo.

DISCUSSION

Results suggest that in ADAD LBP occurs later than AD pathology and often as amygdala‐ or olfactory‐predominant LBP, for which CSF α‐synuclein SAA has low sensitivity.

Highlights

Cerebrospinal fluid (CSF) real‐time quaking‐induced conversion (RT‐QuIC) detects misfolded α‐synuclein in ≈ 10% of symptomatic autosomal dominant Alzheimer's disease (ADAD) patients.

CSF RT‐QuIC does not detect α‐synuclein seeding activity in asymptomatic mutation carriers.

Lewy body pathology (LBP) in ADAD mainly occurs as olfactory only or amygdala‐predominant variants.

LBP develops late in the disease course in ADAD.

CSF α‐synuclein RT‐QuIC has low sensitivity for focal, low‐burden LBP.
Single‐cluster Functionalized TiO2 Nanotube Array for Boosting Water Oxidation and CO2 Photoreduction to CH3OH
Authors: Xu Shen‐Yue , Shi Wenxiong , Huang Juan‐Ru , Yao Shuang , Wang Cheng , Lu Tong‐Bu , Zhang Zhi‐Ming
Published: April 2024

Solar‐driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi‐electron transfer. Single‐cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells‐Dawson‐ and Keggin‐type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single‐cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M=Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface‐hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2‐1 exhibits the highest electron consumption rate of 1260 μmol g−1 for CO2‐to‐CH3OH conversion with H2O as the electron source, which is 11 times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single‐dispersion of molecular cluster to enrich surface‐reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction.
2D Conjugated Metal–Organic Frameworks Bearing Large Pore Apertures and Multiple Active Sites for High‐Performance Aqueous Dual‐Ion Batteries
Authors: Bao Pengli , Cheng Linqi , Yan Xiaoli , Nie Xinming , Su Xi , Wang Heng‐Guo , Chen Long
Published: April 2024

2D conjugated metal–organic frameworks (2D c‐MOFs) with large pore sizes and high surface areas are advantageous for adsorbing iodine species to enhance the electrochemical performance of aqueous dual‐ion batteries (ADIBs). However, most of the reported 2D c‐MOFs feature microporous structures, with few examples exhibiting mesoporous characteristics. Herein, we developed two mesoporous 2D c‐MOFs, namely PA‐TAPA−Cu‐MOF and PA‐PyTTA−Cu‐MOF, using newly designed arylimide based multitopic catechol ligands (6OH‐PA‐TAPA and 8OH‐PA‐PyTTA). Notably, PA‐TAPA−Cu‐MOF exhibits the largest pore sizes (3.9 nm) among all reported 2D c‐MOFs. Furthermore, we demonstrated that these 2D c‐MOFs can serve as promising cathode host materials for polyiodides in ADIBs for the first time. The incorporation of triphenylamine moieties in PA‐TAPA−Cu‐MOF resulted in a higher specific capacity (423.4 mAh g−1 after 100 cycles at 1.0 A g−1) and superior cycling performance, retaining 96 % capacity over 1000 cycles at 10 A g−1 compared to PA‐PyTTA−Cu‐MOF. Our comparative analysis revealed that the increased number of N anchoring sites and larger pore size in PA‐TAPA−Cu‐MOF facilitate efficient anchoring and conversion of I3−, as supported by spectroscopic electrochemistry and density functional theory calculations.
Innovation of some novel complexes based on 1‐(4‐nitrophenyl)‐1H‐1,2,3‐triazol‐4‐yl)methanol ligand: Synthesis, structural elucidation DFT calculation and pharmaceutical studies
Authors: Al‐Abdulkarim Hessah A. , Qasem Hamza A. , Aouad Mohamed Reda , Khushaim Muna S. , Al‐Farraj Eida S. , Abdou Aly , Abu‐Dief Ahmed M.
Published: April 2024

Novel divalent chelates of Co (II), Cu (II), Zn (II) and Ni (II) were prepared and described of the form [M (NTM)(CH3COO)2] where NTM = [1‐(4‐nitrophenyl)‐1H‐1,2,3‐triazol‐4‐yl)methanol ligand. Elemental analyses, infrared red, 1H and 13CNMR, electronic, magnetic susceptibility, conductivity measurements and X‐ray diffraction studies were used to assess our divalent metal complexes. Moreover, the stability and stoichiometry of the novel metal chelates were examined through the job's method in solutions. Correlation of all spectroscopic techniques states that NTM acts as a bi‐dentate NO ligand to afford octahedral complex geometry for all the investigated metal chelates. Thermodynamic and kinetics factors for various thermal degradation phases were calculated. Moreover, B3LYP/LANL2DZ/6‐311 g(d,p) theoretical study has been applied for estimating the MEP and quantum chemical reactivity descriptors of studied molecules. Moreover, the UV–Vis absorption spectra for the investigated molecules are predicted via the time‐dependent DFT (TD‐DFT) calculations. In addition, MOE‐ docking was tested on two different proteins, the receptor of (3HB5) breast cancer mutant oxidoreductase as well as the receptor of Glucosamine‐6‐phosphate synthase in complex with glucosamine‐6‐ phosphate of (2VF5) E.coli and COVID‐19 protease. The results recommended that the (NTMCo), (NTMNi), (NTMCu) and (NTMZn) complexes showed the highest inhibitory activity compared to the other NTM ligands as antimicrobial and breast cancer candidates. Furthermore, in‐vitro anti‐bacterial, anti‐fungal, cytotoxic and anti‐oxidant performances for the selected ligand as well as its chelates were studied. All metal chelates presented superiority, proceeding free organic ligand ineffective management, definitely NTMCu complex.